Herbicidal compositions and methods

ABSTRACT

Certain substituted cyanobenzeneacetonitriles, and their halobenzyl halide intermediates are effective preemergence and postemergence herbicides, which control undesired vegetation without injury to crops.

United States Patent 1 Martin Apr. 15, 1975 HERBICIDAL COMPOSITIONS AND [56] References Cited METHODS UNITED STATES PATENTS [75] Inventor: Elmore Louis Martin, Wilmington, 3,290,353 12/1966 Battershell et a1 260/465 Del. 3,307,933 3/1967 Sasse et a1. 71/105 Assignee: E. II du Pont de Nemours and Com- 3,574,594 GOUgh et 3]. 71/105 pany, Wilmington, Del.

[22] Filed: 1972 Primary ExaminerLewis Gotts 21 APPL 241 49 Assistant ExaminerCatherine L. Mills Related U.S. Application Data [63] Continuation-impart of Ser. No. 201,995, Nov. 24,

1971, abandoned. [57] ABSTRACT Certain substituted cyanobenzeneacetonitriles, and [52] their halobenzyl halide intermediates are effective pre- 30/ emergence and postemergence herbicides, which con- II C A01 9/20 trol undesired vegetation without injury to crops. 58 Field of Search 71/105 6 Claims, No Drawings 1 HERBICIDAL COMPOSITIONS AND METHODS CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part of my copending application Ser. No. 201.995. now abandoned filed Nov. 24, 197 I.

BACKGROUND OF THE INVENTION This invention relates to a class of substituted cyanobenzeneacetonitriles and their halobenzyl halide intermediates, to the use of both classes of compounds as herbicides, and to herbicidal compositions containing them as active ingredients.

US. Pat. No. 3,574,594 (to Gough et. al.) discloses that unsubstituted cyanobenzeneacetonitriles and trifluoromethylbenzeneacetonitriles are useful preemergence herbicides. Those compounds appear. however. to be only moderately active and quite nonselective.

Although a large number of herbicides are presently on the market, there is a continual need for more active, more selective, and reasonably priced herbicides that could be used in the presence of commercial crops.

SUMMARY OF THE INVENTION corn, and rice. These compounds are represented by Formula (I wherein A and B are different, one being a 2 group and the other being a CR -,R,;Z radical; wherein R and R; are each independently hydrogen or methyl, and Z is the cyano group or halogen; and

each of R R R and R independently is hydrogen, a CC; alkyl, a halogen, or the nitro group;

provided that:

a. at most two of R R R and R are nitro groups;

b. at most two of R,, R R and R, are halogens;

c. at least one of R R R and R is hydrogen or halogen;

d. at least one of R,, R R and R is a C -C alkyl;

e. no nitro groups are ortho to each other;

f. no alkyl groups are ortho to each other;

g. each alkyl group has at most three carbon atoms in a straight chain from the point of attachment to the aromatic ring; and

h. when Z is halogen, both R; and R must be hydrogens.

The halobenzyl halide compounds are intermediates in the synthesis of the above cyanobenzeneacetonitriles. Although not as active as the cyanobenzeneacetonitriles, these intermediates also are useful as selective herbicides for control of annual grass weeds in crops.

DETAILED DESCRIPTION OF THE INVENTION Compounds of Formula l can be prepared by many process based on methods generally well known in the art. Simple cyanobenzeneacetonitriles can be made, for instance, by bromination of the corresponding dialkylbenzenes. chloromcthylation of the resulting bromodialkylbenzenes, and replacement of the halogens with cyano groups. This reaction is illustrated by the follow-,

ing equations.

mononitro or dinitro compound, e.g.,

CN NCCHg CN Nitration is carried out by well-known methods. concentrated nitric acid and nitronium tetrafluoroborate being suitable nitrating agents.

Halogenated cyanobenzeneacetonitriles can be ob tained from the dialkylbenzyl halides. as shown below:

CH Cl Br Amen CH CN Preferred because of ease of synthesis and high activity are the compounds offormula (2), below:

CH CN wherein R. and R are each independently alkyl of 2-5 carbon atoms, chlorine, bromine. or the nitro group.

corresponding 2.4-dihalo-3,6-

It will be noted that the compounds of Formula (2) are those compounds of Formula 1') wherein A is the cyanomethyl group; B is the cyano group: and each of R and R ishydrogen.

The most active are those compounds of Formula (2) wherein R is alkyl of 3-5 carbon atoms or the nitro group. and

R is alkyl of 3-5 carbon atoms.

The same order of preference applies to the corresponding halobenzylhalide intermediates for the same reasons.

The compounds of this invention are useful as selective pre-plant incorporated, preemergence, or postemergence herbicides. They provide control of many weeds with excellent selectivity in such crops as corn, soybeans, wheat, cotton and rice. The compounds are most advantageously applied preemergence at rates of 0.25 to pounds per acre, depending on the crop, the weed to be controlled. the soil and environmental conditions and the particular chemical used. Under certain conditions, such as lack of rainfall for an extended period after application, it is advantageous to lightly incorporate these compounds into the soil. Selected members of this class of compounds have postemergence activity and may be used at rates of 1 to 10 kg./ha. for postemergence weed control, if applied while susceptible weeds are young, preferably in the two-leaf stage of development. Two or more compounds of this invention may be applied simultaneously.

Weeds controlled include crabgrass (Digital-1a spp), harnyara'grass (Eclzinochlaa crusgalli), junglerice (Echilmc'h/ua mlonum), foxtail (Setaria $1217.), wilt/zgrass (Panicum capillare), goosegrass (Eleusina imlica), pigweed (Amaram/zus retro/Yarns), wild mustard (Bras- .rica .s'pp), curly dock (Rumax crispus), johnsongrass (Sorghum lzalepanse) from seed, cheat (Bramus secalinus), downy brome (Bromus Iecmrum) and blackgrass (A laput'urus n1 \'sm'0ida.s

It is sometimes advantageous to combine a compound of this invention with another herbicide in order to increase the spectrum of weeds controlled and to minimize the chances of injury to the current or subsequent crops. The exact combination which may be used to the best advantage will depend upon the crop, the weeds to be controlled and the environment in which the crop is growing, but can be readily selected by one with ordinary skill in the art. The use of these herbicides in combination with the herbicides of this invention will provide control of a wide variety of broadleaved weeds including ragweed (Ambrosia spp. 1ambsquarter (Clzanapudium album), morningglory (Ipomea $1112.), sicklepod (Cassia ablusifolia smartweed (P01 \'ganum spp. flower-of-an-hour (Hibiscus rrionum), cocklebur (XanI/zium .s'pp.), and velvetleaf (Abutilon theop/zrasti), as well as grasses.

The herbicidal compositions of this invention containing mixtures with other herbicides can be formulated as such. Alternatively, the compounds of Formula (1 may be tank-mixed with other known herbicides or applied sequentially with other known herbicides.

Among the known herbicides which can be combined with the compounds of Formula (1) are:

SUBSTITUTED UREAS 4 3-(3.4-dichlorophenyl)-3-methox'y-1,l-dimethylurea 3-(4-chlorophenyl)-3-methoxy-1,1-dimethylurea 3( 3 ,4-dichlorophenyl)-1-n-butyl-l-methy1urea 3-( 3,4-dichloropheny1)-1 -methoxy-1 -methylurea 3-(4-chlorophenyl)-l-methoxy-1-methylurea 3-(3.4-dich1orophenyl)-1 ,1 ,S-trimethylurea 3-(3.4-dich1orophenyl)1,l-diethylurea 3-(p-chlorophenoxyphenyl)-1,1-dimethylurea N-cyclooctyl-N'-dimethy1urea 3-(4-chlorophenyl)-1-methyl-1-( 1-methyl-2- propynyl)urea 3-(4-bromo-3-chlorophenyl)-1-methoxy-1- methylurea 3-[p-(p-ch1orophenoxy)phenyl]-1,l-dimethylurea 3-(4-trifluoromethylphenyl)-1,1-dimethylurea 3-(4-bromophenyU-1-methoxy-1-methy1urea 3-(hexahydro-4,7-methanoindan-5-yl)-1,1-

dimethylurea 1-( 2-methy1cyc1ohexyl )-3-phenylurea 3-(p-cumenyl)-1,l-dimethylurea These ureas can be mixed with the compounds of Formula (1) in weight proportions of from 1:40 to 10:1, the preferred ratio being 1:12 to 4:1.

SUBSTITUTED TRIAZIN ES 2chloro-4,6-bis(ethylamino)-s-triazine 2-chloro-4-ethylamino-o-isopropylamino-s-triazine 2-ch1oro-4,6-bis(methoxypropylamino)-s-triazine 2-methoxy-4,6-bis( isopropylamino )-s-triazine 2-diethylamino-4-isopropy1acetamido-6-methoxy-striazine Z-isopropylamino-4-methoxyethylamino-6- methylmercapto-s-triazine 2-methylmercapto-4,6-bis( isopropylamino )-striazine Z-methylmercapto-4,6-bis(ethylamino)-s-triazine 2-methylmercapto-4-ethylamino-o-isopropylaminos-triazine 2-methoxy-4,6-bis(ethylamino)-s-triazine 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4.6-bis( isopropylamino )-s-triazine 2-methoxy-4.6-bis( isopropylamino )-s-triazine 2-ethylamino-4-isopropylamino-fi-methylmercaptos-triazine 2-chI0ro-4-ch1oropropylamino-6-isopropylamino- 1,3,5-triazine 2,4-bis( isopropylamino )-6-methylmercapto-striazine 2-tert-butylamino-4 ethyIamino-6-methyIthio-striazine These triazines can be mixed with the compounds of this invention in the weight proportions of from 1:40 to 10:1, the preferred ratio being 1:12 to 4:1.

PHENOLS 3,5-dinitro-o-creso1 4,6-dinitro-o-sec-butylphenol and its salts 4.6-dinitro-o-sec-amylphenol pentachlorophenol and its salts These phenols can be mixed with the compounds of this invention in the weight proportions of from 1:10 to 10:1, the preferred ratio being 1:5 to 5:1.

SUBSTITUTED URACILS 3-isopropyl-5-bromo-6-methyluraci1 5-bromo3-sec-butyl-6-methyluracil 3-tertbuty1-5-chloro-6-methyluracil 5-chloro-6-methy1-3-neopenty1uracil 3-tert-butyl-5-bromo-6-methyluracil 3isopropyl-5-chloro-6-methyluracil 3-tert-butyl-5-chloro-6-ethyluracil 3-tert-butyl-S-chloro-6-chloromethyluraeil 3-cyclohexyl16-methyluracil 3-cyclohexyl-6 ethylulraci1 3-cyclohexyl-o-sec-butyluracil 3-norbornyl-6-methyluracil 3-cyclopentyl-o-methyluracil 3-cyc1ohexy1-6-isopropy1uracil 3-cye1ohexyl-5,6-trimethyleneuracil 3-sec-butyl-5,6-trimethyleneuraci1 3-isopropy1-5,-trimethyleneuracil 3-isopropy1-5,o-tetramethyleneuracil 3-isopropy1-5,o-pentamethyleneuracil 3-cyclohexyl-5-bromouracil 3-cyc1ohexyl-5-ch1orouraci1 3-isopropyl-S-bromouracil 3-sec-butyl-5-bromouracil 3-sec-butyl-5-chlorouracil 3-isopropy1-1-trichloromethylthio-5-bromo-6- methyluracil 3-cyclohexyl-1-trichloromethylthio-5-bromo-6- methyluracil 3-sec-butyl-1-acetyl-5-bromo-6-methyluracil 3-isopropy1-1-acetyl-5-bromo-6-methyluracil 3-isopropy1-1-trich1oromethylthio-5-chloro-6- methyluracil These substituted uracils can be mixed with the compounds of this invention in the weight proportions of from 1:80 to :1, the preferred ratio being from 1:20 to 4:1.

CARBOXYLIC ACIDS AND DERIVATIVES The following carboxylic acids and derivatives can be mixed with the compounds of this invention in the listed weight proportions:

A. 2,3.6-trichlorobenzoic acid and its salts 2,3.5.6-tetrachlorobenzoic acid and its salts 2-methoxy-3,5,o-trichlorobenzoic acid and its salts 2-methoxy-3,o-dichlorobenzoic acid and its salts 2-methoxy-3,5,o-trichlorobenzoie acid 3-amino-2,S-dichlorobenzoic acid and its salts 3-nitro-2,5-dichlorobenzoic acid and its salts 2-methy1-3,o-dichlorobenzoie acid and its salts 4-chlorophenoxyacetic acid and its salts and esters 2,4-dichlorophenoxyacetic acid and its salts and esters 2.4-dichlorophenoxyethylsulfate 2,4,5trichlorophenoxyacetic acid and its salts and Mixed in a 1:40 to 4:1 ratio, preferably a 1:16 to 3:1

ratio. C. trichloroacetic acid and its salts Mixed in a 1:8 to 8:1 ratio, preferably a 1:4 to 4:1 ratio. D. 2,2-diehloropropionic acid and its salts 2( oz-naphthoxy-N,N-diethylpropionamide 2-( 4-ch1oro-6-ethylamino-2-ylamino )methylpropionitrile Mixed in a 1:8 to 8:1 ratio, preferably a 1:4 to 4:1 ratio. E. N,N-di(n-propy1)thiolcarbamic acid, ethyl ester N.N-di(n-propyl)thiolcarbamic acid, n-propyl ester N-ethyl-N-(n-butyl)thiolcarbamie acid, ethyl ester N-ethyl-N-(n-butyl)thiolearbamic acid, n-propyl ester S-2,3-dichloroallyl-N,N-diisopropylthiolcarbamate S-2,3 ,3-trich1oroallyl-N,N-di-isopropylthiolcarbamate S-propyl-n-butylethylthiocarbamic acid 2-chloroallyldithiocarbamate S-ethyl diisobutylthiocarbamate 2-chloroally1diethyldithioearbamate S-cthyl-N-ethylthiocyclohexanecarbamate Mixed in a 1:4 to 4:1 ratio, preferably a 1:2 to 2:1 ratio. F. N-phenylcarbamic acid, isopropyl ester N-(m-ehlorophenyl)carbamic acid, isopropyl ester N-(m-chlorophenyl)carbarnic acid, 4-chlor0- 2-butynyl ester N-(3,4-dichlorophenyl)carbamic acid, methyl ester N-( 3,3-dimethylureido )phenyl-tert-butylcarbamate 2,o-di-tert-butyl-p-tolylmethylcarbamate Mixed in a 1:8 to 8:1 ratio, preferably a 1:4 to 4:1 ratio. G. 2,3,o-trichlorophenylacetic acid and its salts Mixed in a 1:4 to 8:1 ratio, preferably a 1:4 to 4:1 ratio. H. 2-chloro-N,N-diallylacetamide maleic hydrazide 1,2-dihydropyridazine-3 ,6-dione 3', 4'-dichloro-Z-methacrylanilide 2-chloro-2, 6'-diethyl-N-(methoxymethylacetanilide N-( butoxymethyl )-2-ch1oro-2', 6'-diethylacetanilide 3,5-dinitro-N,N'-dipropy1sulfanilamide 2-chloro-N-isopropylacetanilide 3, 4-dichloropropionanilide,

Mixed in a 1:8 to 10:1 ratio, preferably a 1:4 to 5:1

ratio. 1. 4-amino-3,5,6-trich1oropicolinic acid Mixed in a 1:100 to 4:1 ratio, preferably a 1:20 to 2:1

ratio.

' INORGANIC AND MlXEDlNORGANlC-ORGANIC SALTS The following salts can be mixed with the compounds of this invention in the listed weight proportions:

A. monoammonium methanearsonate calcium methylarsonate tio. B. sodium arsenite potassium cyanate 7 Mixed in a 1:10 to 20:1 ratio, preferably a 1:5 to 10:1

ratio. C. lead arsenate calcium arsenate Mixed in a 10:1 to :1 ratio, preferably a 20:1 to

50:1 ratio. D. sodium tetraborate hydrated, granulated sodium metaborate sodium pentaborate polyborchlorate unrefined borate ore such as borascu Mixed in a 10:1 to 600:1 ratio, preferably a 20:1 to

400:1 ratio. E. ammonium thiocyanate Mixed in a 1:10 to 10:1 ratio, preferably a 1:5 to :1

ratio. F. sodium chlorate Mixed in a :1 to 200:1 ratio, preferably a :1 to

100:1 ratio. G. ammonium sulfamate Mixed in a 1:1 to 200:1 ratio, preferably a 2:1 to

100:1 ratio.

OTHER ORGANIC HERBlClDES These organic herbicides can be mixed with compounds of this invention in the listed weight proportions: A. 6,7-dihydroipyrido]1,2-a;2', 1'- c]pyrazinediium ion 1,1'-dimethyl-4,4-bipyridinium ion Mixed in a 1:20 to 10:1 ratio, preferably a 1:10 to 5:1

ratio. B. 3-amino-l ,2,4-triazole Mixed in a 1:20 to :1 ratio, preferably a 1:10 to 10:1 ratio. C. 3,6endoxohexahydrophthalic acid Mixed in a 1:10 to 20:1 ratio, preferably a 1:4 to 10:1

ratio. D. hexachloroacetone Mixed in a 1:8 to 16:1 ratio, preferably a 1:4 to 8:1

ratio. E. diphenylacetonitrile N,N-dimethyl-a.a-diphenylacetamide N,N-di-n-propyl-2,6-dinitro-4-trifluoromethylaniline N,N-di-n-propyl-2,6-dinitro-4-methylaniline 2,6-dinitro-N,N-di(2-chlorocthyl)-p-toluidine 4-(mcthylsulfonyl)-2,6-dinitro-N.N-dipropylaniline N-sec-butyl-4-tcrt-butyl-2,6-dinitroaniline 4-isopropyl-2,6-dinitro-N,N-dipropylaniline Mixed in a 1:10 to 10:1 ratio, preferably a 1:5 to 5:1

ratio, F. .-(2,4-dichlorophenyl)-O- methylisopropylphosphoramidothiate 0.0- diisopropylphosphorodithioate-S-ester with N- (Z-mercaptoethyl)benzenesulfonamide S-ethylhexahydro-l-H-azepine-l-carbothioate 2,3,5,o-tctrachloroterephthalic acid, dimethyl ester Mixed in a 1:20 to 20:1 ratio, preferably a 1:10 to 10:1 ratio. G. 2,4-dichlorophenyl-4'-nitrodiphenyl ether Starting Material Z-hromoethylhenzene Z-bromoisop ropylbenzene Z-bromo-sec-hulylhenzene Z-hromo-tert-hutylhenzene Z-hromoisobutylbenzene 3-bromoethylhenzene 3-hromo-( l. l .2.Z-tetramethylpropyl )benzcne J-hromoisopropylbenzene 3-hromo-sec-butylbenzene 3-bromo-tert-butylbenzene 3-hromoisohutylhenzene 8 2,4-dinitro-4-trifluoromethyldiphenylether Mixed in a 1:20 to 10:1 ratio, preferably a 1:10 to 5:1

ratio. H. N-l-naphthylphthalamic acid and its salts Mixed in a 1:8 to 20:1 ratio, preferably a 1:4 to 10:1 ratio. 1. 3-chloro-2 methyl-p-valerotoluididc 2-chloro-N-(ethoxymethyl)-6'-ethyl-O- acetotoluidide N-butyl-N-ethyl-a, a, toluidine Mixed in a 1:10 to 10:1 ratio, preferably a 1:5 to 5:1

ratio. J. 3,3a-dihydro-2-(p-methoxyphenyU-SH- pyrazolo( 5, l -A )-isoindol-8-one 2-[3-(4-methoxyphenyl)-5-pyrazolyl)]benzoic acid 2-(3-phenyl-5-pyrazolyl)benzoic acid Mixed in a 1:20 to 8:1 ratio, preferably a 1:10 to 4:1

ratio.

The preparation of representative halobenzyl halides and cyanobenzeneacetonitriles is illustrated in the following examples, wherein all parts, proportions, and percentages are per weight unless indicate otherwise.

EXAMPLE 1 3Bromo-4-isopropylbenzyl Chloride 3-Bromo-2-isopropylbenzyl Chloride. and

4-Bromo-3-isopropylbenzyl Chloride lnto a mechanically stirred mixture of 99 parts of Z-bromoisopropylbenzene, 20 parts of paraformaldehyde, and 10 parts of zinc chloride is passed a rapid stream of dry hydrogen chloride at 60C. The mixture is stirred for 3 hours at 50-60C, then cooled and diluted with methylene chloride. The methylene chloride mixture is filtered. The filtrate is washed with dilute hydrochloric acid and dilute sodium bicarbonate until neutral, dired and concentrated, The residue is chromatographed on Florisil or alumina and 3-bromo-4-isopropylbenzyl chloride, 3-bromo-2-isopropylbenzyl chloride, and 4-bromo-3-isopropylbenzyl chloride are isolated as three of the fractions.

The following benzyl chlorides are prepared from the listed alkylhalobenzenes by the method described in the above example. Where isomeric mixtures are formed, the isomers are separated by chromatography or fractional distillation.

TABLE 1 Product 3hromo-4-ethylbenzyl chloride 3-bromo-2-cthylbenzyl chloride 4-hromo-3-ethylbenzyl chloride 3-bromo-4-isopropylbenzyl chloride 3-bromo-2-isopropylbenzyl chloride 4-hromo-3-isopropylhenzyl chloride 3-hromo-4-sec-butylbenzyl chloride 3-bromo-2-sec-butylbenzyl chloride 4-hromo-3-sec-butylbenzyl chloride 3-bromo-4-tert-hutylbenzyl chloride 3-hromo-Z-tert-hutylbenzyl chloride 4-hromo-3-tert-hutylbenzyl chloride 3-bromo-4-isobutylbenzyl chloride 3-hromo-2-isobutylbenzyl chloride 4-bromo 3isobutylbenzyl chloride 2-hromo-4-ethylbenzyl chloride 4bromo-Z-ethylhenzyl chloride 3-bromo-5-ethylhenzyl chloride 2-bromo-4-( 1. l .2.2-tetramethylpropyl )benzyl chloride 4-bromo-2-( 1.12,2-tetramethylpropyl)benzyl chloride 3-hromo-5-( 1,1.2.2-telramethylpropyl)henzyl chloride 2-hromo-4-isopropylbenzyl chloride 4-hromo-2-isopropylbenzyl chloride 3-hromo-S-isopropylhenzyl chloride 2-bromo-4-sec-butylbenzyl chloride 4-hromo-2-sec-butylbenzyl chloride 3-bromo-S-sec-hutylbenzyl chloride 2 bromo-4-tert-butylbenzyl chloride 4-bromo-2-tert-hutylhcnzyl chloride 3-bromo-S-tert-butylbenzyl chloride 2-hromo-4-isohutylhenzyl chloride TABLE I Continued Starting Material Product 4-hromo-Z-isohutylbenzyl chloride B-hromo-S-isohut lhenzyl chloride -hromo-2-ethylbenzyl chloride 2-hromo-5-ethylbenzyl chloride S-hromo sopropylhenzyl chloride 2-bromo-5-rsopropylbenzyl chloride S-hromoJ-sec-hutylhenzyl chloride Z-hromo-S-sec-hutylbenzyl chloride V 5-hromo-Z-tert-hutylhenzyl chloride 2-hromo-5-tert-hutylhen2yl chloride 4-hromocthylhenzene 4-bromoisopropylbenzene 4-hromo-sec-hutylhenzene 4-hromo-te rt-hutylhenzene 4-bromoisohutylbenzene S-hromosohutylhenzyl chloride Z-hromo-Sdsohutylbenzyl chloride I 4-hromo-( l. l .2.Z-tetramethylpropyl)benzene 5-hromo-2-( l.l .2.2-tetramethylpropyl)henzyl chloride 2-hromo-5-( l. l .2.Z-tetramethylpropyl )benzyl chloride 2-hromo-( l.l .2.Z-tetramethylpropyl)henzene 3-hromo-4-( l.l.LZ-tetramethylpropyl)benzyl chloride 3-hromo-2-( l. l .lZ-tetramethylpropyl )benzyl chloride -l-hromo-f -l l.l .ll-tetramethylpropyl )benzyl chloride 2-iodoisopropylbenzene 3-iodo-4-isopropylhenzyl chloride 3-iodo-2 sopropylhenzyl chloride 4-iodoJ-isopropylhenzyl chloride 2-fluoroisohutylhenzene 3-fluoro-4-isohutylhen2yl chloride 3-fluoro-2 'sohutylbenzyl chloride -l-fluoro-3-rsohutylbenzyl chloride 3-ethyliodobenzene Z-eIhyL-l-iodohenzyl chloride 4-ethyl-2-iodohenzyl chloride 3-ethyl-5-iodohenzyl chloride 3-sec-hutylfluorohenzene 2-sec-hutyl-4-fluorohenzyl chloride 4-sec-butyl-Z-fluorobenzyl chloride 3-sec-hutyl-S-fluorohenzyl chloride 4-tert-butyliodohenzene II-tert-hulyl-dodohenzyl chloride S-tert-hutyl-2-iodohenz 'l chloride 4-fluoropropylbenzene 5-fluoro-Z-propylhenzyl chloride Z-fluoro-S-propylhenzyl chloride Z-chloroisopropylhcnzene 3-chloro-4-isopropylbenzyl chloride 3-chloroJ-isopropylbenzyl chloride 4-chloro-3-isopropylbenzyl chloride 3-chloroisohutylbenlyl chloride 4-chloro-2-isobut \'lbenzyl chloride 2-chloro-4-isohutylbenzyl chloride 3-chloro-5-isobutylhcnzyl chloride 4-chloro-( l.l.2.Z-tetramethylpropyl)henzyl chloride 5-chloro-2-( l.l.2.2-tetramethylpropyl)henzyl chloride 2-chloro-5-( l. l .2.Z-Ietramethylpropyl )henzyl chloride Eleven grams of chlorine is slowly passed in under the surface at C. The methylene chloride solution is To a mechanically stirred mixture of parts of separated, washed with dilute hydrochloric acid. then 4-bromo-Lisopropylbenzyl chloride and 50 parts of N- with 5 percent sodium bicarbonate and water, dried methylpyl'rdlidone is added 22 Parts of cupl'ous y and concentrated. The residue is chromatographed and nide- The mixture is rapidly heated to 200C and kept 40 4-cyano-3-isopropylbenzeneacetonitrile is isolated as at 2052l0C for 1 hour, then cooled and transferred one of the fractions to a beaker containing ice and water. The mixture is stirred in a Waring blender. collected on a filter and The following cyanobenzeneacetonitriles are prewashed with cold water. The thick paste is suspended pared from the listed benzyl chlorides by the above in water, and 100 parts of methylene chloride is added. procedure.

EXAMPLE 2 4-Cyano-3-isopropylbenzeneacetonitrile TABLE II Starting Material Product 3-hromo-4-isopropylhenzyl chloride 3-cyano-4-isoprop 'lhenzeneacetonitrile 3-hromo-4-sec-hutylhenzyl chloride 4-scc-hulyl-3-cyanohenzeneacetnnitrile 3-hromo-4-tert-hutylhenzyl chloride 4-tert-hutyl-3-cyanohenzeneacetonitrile. m.p. "IS-766C 3-hromo-4-isohutylhenzyl chloride 3-c 'nano-4-isohutylhenzeneacetonitrile 3-bromo-4-ethylbenzyl chloride 3-cyan0-4-ethylhenzeneacetonitrile 3-hromo-2--prop 'lbenzyl chloride 3-cyano-2-propylhenzeneacetonitrile 3-bromo-Z-sec-hutylhenzyl chloride 2-scc-butyl-3-c)anohenzeneacetonitrile 3-bromo-2-tert-hutylhenzyl chloride Z-tert-butyl-3-cyanohcnzeneacetonitrile 3-hromo-2-isohutylhenzyl chloride 3-cyanoisohutylhenzeneacelonitrile 3- soprop \'lhenzyl chloride 3-cyanosopropylhenzeneacetonitrile 4-bromo-3-isopropylhenzyl chloride 4-cyano-. 'sopropylhenzeneacetonitrile 4-hromo-3-( l.l .2.Z-tetramethylpropyl)benlyl chloride 4-cyano-3-( l.l -tetrameth \'lpropyl)benzeneacetonitrile 4-bromo-3-sec-hutylhenzyl chloride 3-sec-butyl-4-c nohenzeneacetonitrile 4-hromo-3-terthutylhenzyl chloride 3-tert-hut -l-4-cyanohenzeneacetonitrile 4-hromo-3-isobutylbcn2yl chloride 4-cyan0-3-isobutylhenzeneacetonitrile 4-cyano-Z-ethylbenzcneacetonitrile 4-hromo-2-ethylhenzyl chloride 4-cyant2-rsopropylbenzeneacetonnrrle 4-bromo-Z-isopropylhenzyl chloride 4-hromo-Z-sec-hutylbenzyl chloride 2-sec-but l-4-cyanohenzeneacetonitrile 4-hromo-2tert-hutylhenzyl chloride 2-tert-hutyl-4-cyanohenzeneacetonitrile 4-bromo-Z-isohutylbenzyl chloride 4-cyano-l-isobutylbenzeneacetomtrile 5-cyano-2-isoprtmpylhenzeneacetonitrile 5-bromo-Z-isopropylhenzyl chloride Z-scc-hut -l-5-cyanobenzeneacetonnrile 5-hromo-2-sec-hutylbenzyl chloride 5-bromo-Z-tert-hutylbenzyl chloride 2-tert-butyl-5-cyanohenzeneacetonitrile 5-hromo-2-isohutylhcnzyl chloride 5-cyano-2-isobutylhenzencacetonitrile 5-bromo-2-propylhenzyl chloride 5-cyano-Z-propylhenzencacetonitrile 3-bromo-5-( I.l.2.Z-tetramcthylpropyl)benzyl chloride 3-cyano-5-l l.l.2.2-tetramethylpropyl)benzeneacetonitrile EXAMPLE 3 4-Bromo-2-chloro-5-ethylbenzyl Chloride, 4-Bromo-Z-chloro-3-ethylbenzyl Chloride, and

4-Bromo-3-chloro-5-ethylbenzyl Chloride 5 ethylbenzyl chloride are isolated as three of the frac- To a solution of 46 parts of 4-bromo-3-ethylbenzyl tions. chloride and 3 parts of iodine in 300 parts of chloro- The following alkyldihalobenzyl chlorides are preform is added 16 parts of chlorine. The solution is repared from the appropriate alkylmonohalobenzyl chlofluxed in the absence of light for 6 hours, then cooled rides by the above method. Where isomeric mixtures and extracted with water and dilute sodium bisulfite so- 10 are obtained. the isomers are separated by chromatoglution. The organic phase is separated, dried and conraphy.

TABLE Ill centrated. The The residue is chromatographed on Florisil or alumina and 4-bromo-2-chloro-5- ethylbenzyl chloride, 4-bromo-2-chloro-3-ethylbenzyl chloride. and a small amount of 4-bromo-3-chloro-5- Starting Material Product 4-hromo-3-isopropylhenzyl chloride 4-bromo-3-isohutylhenzyl chloride 4-bromo-3sec-butylhenzyl chloride 4-hromo-Z-tert-hutylhenzyl chloride 4-bromo'2-eth \lbenzyl chloride 4-hromo-2-( l. l .2.Z-Ietramethylpropyl )henzyl chloride 3-bromo-Z-isopropylhenzyl chloride 3-hromo-2-sec-butylhenzyl chloride 3-hromo-l-ethylhenzyl chloride 3-hromo-5-( Ll .l2-tetramethylpropyl )henzyl chloride 3-hromo-5-tert-hutylhenzyl chloride 3-hrorho-5-isopropylhen7yl chloride S-hromo-Z-ethylhenzyl chloride 5-hromo-Z-tert-hutylhenzyl chloride S-hromo-2-sec-hutylbenzyl chloride J-hromo-4-isohutylhenzyl chloride 3-hromo-J-isopropylhenzyl chloride S-hromo-4-scc-hutylhenzyl chloride 3-iodo-4-isopropylhenzyl chloride 2-iodo-4-( l. l .2.2-telramethylpropyl )henzyl chloride 5-iodo-h-isohutylhenzyl chloride 4-fluoro-3-isopropylhenzyl chloride 3-tert-hutyl-5-fluorohenzyl chloride 2-ethyl-3-fluorohenzyl chloride 3-bromo-5-( l.l.2.2-lelramethylpropyl )henzyl chloride 4-hromo-3-chloro-5 4-hromo-2-chloro- 4-hromo-2-chloro- 4-hromo-3-chloro- 4-hromo-2-chloroisohutylhenzyl chloride 4-hromo-2-chloro-, -isobutylbenzyl chloride 4-hromo-3-sec-butyl-5-chlorobenzyl chloride 4-hromo sec-hutyl-2-chlorohenzyI chloride -i-bromo sec-hut LZ-chlorobenzyl chloride 4-bromo-Z-tert-butyl-o-chlorohenzyl chloride 4-hromwZ-tert-hutyl-S-chlorohenzyl chloride 4-bromo-2-tertbutyl-3-chlorohenzyl chloride 4-hromo-Z-chloro-(v-ethylbenzyl chloride 4-hromo-5-chloro-Z-ethylbenzyl chloride 4-hromo-3-chloro-2-ethylbenzyl chloride 4-bromo-2-chloro-6-l l l .2.2-tetramethylpropyl )benzyl chloride 4-hromo-5-chloro-2-( l, l .2,2-tetramethylpropyl )henzyl chloride 4-hromo-3-chloro-2-( l .l.2.Z-tetramethylpropyl)benzyl chloride 3-hromo-6-chlorr -isopropylbenzyl chloride 3-hromo-5chloroopropylhenzyl chloride 3-hromo-4-chloro-..-isopropylhenzyl chloride 3-hromo-Z-sec-butylo-chlorobenzyl chloride 3-bromo-Z-sec-hutyl-5-chlorohenzyl chloride 3-bromo-2-sec-butyl-4-chlorohenzyl chloride 3-hromo-fi-chloro-Z-ethylhenzyl chloride 3-hromo-5-chloro-2-ethylhenzyl chloride 3-bromo-4-chloro-Z-ethylhenzyl chloride 5-bromo-2-chloro-3-( l.l .ZJ-tetramethylpropyl )henzyl chloride 3-bromo2-chloro-54 I.l. Z-tetramethylpropyl)henzyl chloride -hromo-4-chloro-5-( l. l 2-tetrameth 'lpropyl )benzyl chloride -hromo-3-tert hutyl Z-chlorobenzyl chloride -hromo-S-tert-butyl-Z-chlorohenzyl chloride -h omo 5 tert hutyl-4-chlorohenzyl chloride -h omo-2-chloro-3-isopropylhenzyl chloride -}l:romo-2-chloroopropylhenzyl chloride h romo-4-chloro qwpropylhenzyl chloride romo-2-chloro-o-ethylhenzyl chloride romo-4-chloro-6-ethylhenzyl chloride romo-3-chloro-2-ethylhenzyl chloride romo-fi-terbhutyI-Z-chlorohenxyl chloride -hromo-2-terthutyl-4-chlorohenzyl chloride hromo-Z-terI-hutyI-S-chlorobenzyl chloride -hromo-6'secbut \'l-2-chlorobenzyl chloride -hromo-Z-sec-hutyl-4-chlorohenzyl chloride -hromo-Z-sec-hut 'l-3-chlorohenzyl chloride -bromo-2-chloro-4-isohutylhenzyl chloride -hromo-Z-chloro4-isohutylhenzyl chloride -hromo-5-chloro-4-isohutylhenzyl chloride -bromo-2-chloro-4-isopropylbenzyl chloride 2romo-2-chloro-4-isopropylbenzyl chloride -h romo-S-chloro-4-isopropylbenzyl chloride romo-4-sec-hutyl-l-chlorohenzyl chloride romo-4-sec-hutyl-2-chlorobenzyl chloride romo-4-sec-butyl-S-chlorohenzyl chloride romo-3-iodo-4-isopropylhenzyl chloride romo-5-iodo-4 ,opropylhenzyl chloride r0mo-5 iodo-4-isoprop}'lhenzyl chloride romo-2-iodo-4( l. l .2.Z-tetramethylpropyl )hcnzyl chloride romo-2-iodo-4-l l.l. -tetramethylpropyl)henzyl chloride romo-6-iodo 4-( l. l .2.Z-terramethylpropyl )henzyl chloride romo-3-iodo-6-isohutylbenzyl chloride romo-S-iodo-Z sobutylhenzyl chloride romo-S-iodo-Z-isohutylbenzyl chloride romo-4-fluoro- -isopropylhenzyl chloride romo-4-fluoroopropylbenzyl chloride romo-4-fluoroopropylhenzylchloride romo-3-tert-hutyl-S-fluorobenzyl chloride romo-3-tert-hut l-5-fluorohenzyl chloride hromo-S-tert-hutyl-3-fluorohenzyl chloride hromo-Z-elhylJ-Huorohenzyl chloride hromo-Z-ethyl-3-fluorohenzyl chloride hromo-2-ethyl-3-fluorohenzyl chloride B-dibromo'S- l. l .ll-tetramethylpropyl )henzyl chloride 4-dihromo-5-l l 5-dihromo-3-( l .l -tctramelh)lpropyl )henzyl chloride .l .2.Z-tetramethylpropyl )henzyl chloride TABLE III Continued Starting Material J-hromo-Z-sec-butylbenzyl chloride EXAMPLE 4 2-Chloro-4-cyano-5-ethylbenzeneacetonitrile To a mechanically stirred mixture of 26 parts of 4- bromo-2-chIoro-S-ethylbenzyl chloride and 50 parts of N-mcthylpyrrolidinone is added 22 parts of cuprous cyanide. The mixture is rapidly heated to 200C and kept Product 3-dihromo-4-isohutylhenzyl chloride 5-dihromo-4-isobutylhenzyl chloride 5-dihromo-4-isohutylhenzyl chloride 5 d' see-hutylhenzyl chloride 5 d sec-hutylhenzyl chloride B-dihromo-(w-sec-hutylbenzyl chloride ride is added. Eleven grams of chlorine is slowly passed in under the surface at 15C, the methylene chloride solution is separated. washed twice with dilute hydrochloric acid, then with 5 percent sodium bicarbonate solution, and with water. The solution is dried, filtered and concentrated. The residue is chromatographed and f 2050-2 10C fm 1 hour Q f and the mixture 20 4-cyano-2-chlo ro-5-ethylbenzeneacetonitrile is isois transferred to a beaker containing ice and water. The latcd as one of the isomers.

mixture IS stirred in a Waring blender, collected on a filter and washed with cold water. The thick paste is The following benzeneacetonitriles are prepared suspended in water and 150 parts of methylene 'chlofrom the listed benzyl chlorides by the above method.

TABLE IV Starting Material -isopropylbenzyl chloride ohutylhenzyl chloride 4-bromo-3-sec-but -chlorobenzyl chloride 4-bromo-3-tert-hut -chlorohenzyl chloride 4-bromo-3-chloroisohutylbenzyl chloride 4-hromo-3-chloro-54 l. l .2.2-tetramethylpropyl )henzyl chloride 4-bromo-5-chloro-2-ischutylbenzyl chloride 4-bromo-5-chloroethylbenzyl chloride 4-bromo-3-chloroisopropylbenzyl chloride 4-bromo-2-sec-butyl-3-chlorohenzyl chloride 4-hromo-2-ehloro-fi-isopropylhenzyl chloride 4-bromo-2-chloro-6-ethylbenzyl chloride 3-bromo-5-chloro-Z-isopropylbenzyl chloride 3-bromo-2-sec-butyl-S-chlorobenzyl chloride 3-bromo-4-chloro-Z-propylbenzyl chloride 3-hromo-4-chloro-Z-isopropylhenzyl chloride 3 bromo-(v-chloro-Z-ethylhenzyl chloride 3-bromo-6-chloro-Z-isohutylbenzyl chloride 5-bromo-3-tert-butyl-Z-chlorohenzyl chloride S-bromo-3-sec-butyl-2-chlorobenzyl chloride 3-hromo-5-tert-hutyl-4-chlorohenzyl chloride 3-hromo-4-chloro-5-isohutylbenzyl chloride 3-hromo-Z-chloro-S-isopropylhenzyl chloride 3-hromo-Z-chlorwS-propylbenzyl chloride 5-hromo-3-chloro-Q-isobutylbenzyl chloride 5-bromo-Z-sec-hutyl-3-chlorobenzyl chloride 3-hromo-4-chloro-fi-ethylhenzyl chloride 3-bromo-4-chloro-o-propylbenzyl chloride 3-hromo-flsec-butyl-2-chlorohenzyl chloride 3-hromo-2-chloro-o-isohutylbenzyl chloride 3-hromo-4-sec-hutyl-S-chlorohenzyl chloride 3-hromo-5-chloro-4-t l.l.2.Z-tetramethylpropyl )henzyl chloride 5hromo-44ert-hutyl-Z-chlorohenzyl chloride 5-hromo-2-chloro-4-ethylbenzyl chloride J-hromo-2-chloro-4-isohutylbenzyl chloride 3-hromo-4-tert-hutyl-Z-chlorohenzyl chloride 2-hromo-3-iodo-4-isopropylhenzyl chloride J-hromo-5-iodo-2-isohutylbenzyl chloride 3-bromo-4-fluorwS-isopropylbenzyl chloride Shromo-Z-ethyl-3-fluorohenzyl chloride 3.5-dihromo-4- obutylbenzyl chloride 4.5-dihromo-Z-sec-hutylbcnzyl chloride 4-bromo-2-chloro-5 4-bromo-2-chloro Product 2-chloro-4-cyano-S-isopropylhenzeneacetonitrile 2-chloro-4-cyano-S-isobutylhenzeneacetonitrile 3-sec-butyl-2-chloro-4-cyanobenzeneacetonitrile 3-tert-hutyl-Z-chloro-4-cyanobenzeneacetonitrile 3-chloro-4-cyano-5-isobutylhenzeneacetonitrile 3-chloro-4-c \'ano-5-( l. l .2.Z-tetramethylpropyl )benzeneacetonitrile 5-chloro-4-cyano-2-isobutylbenzeneacetonitrile 5-chloro-4-cyano-Z-ethylbenzeneacetonitrile 3-chloro-4-cyano-2-isopropylbenzeneacetonitrile 2-sec-butyl-3-chloro-4-cyanobenzeneacetonitrile 2-chloro-4-cyano-fi-isopropylbenzeneacetonitrile 2-chloro-4-cyano-(a-ethylhenzeneacetonitrile 5-chloro-3-cyano-2-isopropylbenzeneaeetonitrile Z-sec-hutyl-S-chloro-3-cyanohenzeneacetontrile 4-chloro-3-cyano-l-propylbenzeneacetonitrile 4-chloro-3-cyano-2-isopropylbenzeneacetonitrile 6-chloro-3-cyano-2-ethylbenzeneacetonitrile b-chloro-B-cyano-Z-isobutylbenzeneacetonitrile 3-ten-hutyI-2-chloro-5-cyanobenzeneacetonitrile 3-sec-hutyl-Z-chloro-S-cyanobenzeneacetonitrile 5-tert-hutyl-4-chloro-3-cyanobenzeneacetonitrile 4-chloro-3-cyano-5-isobutylhenzeneacetonitrile 2-chloro-3-cyano-5-isopropylhenzeneacetonitrile 2-cl1loro-3-cyano-5-propylhenzeneacetonitrile 3-chloro-5-cyano-2-isobutylbenzeneacetonitrile Z-sec-hutyl-3-chloro-S-cyanohenzeneacetonitrile 4-chloro-3-cyano-6-ethylhenzeneacetonitrile 4-chloro-3-cyano-6-propylbenzeneacetonitrile o-sec-hutyl-2-chloro-3-cyanobenzeneacetonitrile Z-chloro-3-cyano-6-isohutylhenzeneacetonitrile 4-sec-hutyl-5-chloro-3-cyanobenzeneaectonitrile 5-chloro-3-cyano-4-( l l .2.Z-tetramethylpropyl )benzeneacetonitrile 4-tert-butyl-Z-chloro-5-cyanobenzeneacetonitrile 2-chloro-S-cyano-4-ethylbenzeneacetonitrile 2-chloro-. -cyano-4-isobutylhenzeneacetonitrile 2-chloro-3 yano-4-isohutylhenzeneacetonitrilc 3 yano-5-iodo-4-iso ropylhenzeneacetonitrile 4-cyano-5-iodo-2-isol:utylhenzeneacetonitrile 3-eyano-4-fluoro-S-isopropylhenzeneacetonitrile S-cyanoQ-ethyl-S-fluorohenzenediacctonitrile 3-hromo'5-cyano-4-isohutylhenzeneacetonitrile S-bromo ec-hutyl-4-cyanobenzeneacetonitrile 4-hromo-Z-sec-hutyl-5-cyanohenzeneacetonitrile EXAMPLE 5 sodium bisulfite, then dried and concentrated. The residue is chromatographed and 3-bromo-2,5-dichloro-4- cthylbenzyl chloride and a small amount of 3-bromo- 2.6'dichloro-4-ethylbenzyl chloride are isolated as two 5 of the fractions.

The following alkyltrihalobenzyl chlorides are prepared from the listed alkyldihalobenzyl chlorides by the above method. Where isomeric mixtures are formed.

10 the isomers are separated by chromatography.

TABLE V Starting Material Product 5-hromo-Z-chloro-4-isopropylhenzyl chloride -hromo-2-chloro-Lisohutylhenzyl chloride -hromo-4-seobutyL2-chlorobenzyl chloride -hromo 2-chloro-4-ethylhenzyl chloride 3-hromo-4scc-hutyl-Z-chlorohenzyl chloride 3-hromo-Z-chloro-fi-propylhenzyl chloride 3-hromo-2-chloro-o-isohutylhenzyl chloride 5-hromo2-terthulyl-4-chlorobenzyl chloride 5-bromo-4-chloro-2-( l. l .ll-tetramethylpropyl )henzyl chloride 4-bromo-2-chloro-6-isopropylbenzyl chloride 4-hromo-Z-chloro-b-isobutylhenzyl chloride 4-bromo-Z-sec-hutyl-3-chlorohenzyl chloride 4-hromo-2 tert-hutyl-3-chlorohenzyl chloride 4-bromo3-ehloro-5-isohutylbenlyl chloride 4-hromo-3'chloro-5-isoprop)'lhenzyl chloride 4-hrom0-2-chloro-3-( l. l .12-tetramethylpropyl )henzyl chloride 4-hromo-3-tert-hutyLZ-chlorohenzyl chloride 3-bromo-6-chloro-Z-isohutylbenzyl chloride 3-hromo-o-chloro-Z-ethylhenzyl chloride S-hromo-3-sec-butyl-Z-chlorohenzyl chloride 5-bromo-3-tert-butyl-Z-chlorohenzyl chloride S-hromo-3-iodo-4-isobutylbenzyl chloride 5-hromo-3-fluoro-4-isopropylbenzyl chloride 3.S-dibromo-4-isopropylhenzyl chloride 3-bromo-4iodo-5-isobutylbenzyl chloride 3-hrom0-4-fluoro-5-isopropylhenzyl chloride 3.4-dibromo-5-isopropylbenzyl chloride 3-bromo-2-tert-hutyl-4-chlorobenzyl chloride 3-brorno-Z-sec-butyl-4-chlorohenzyl chloride 3-bromo-4-chloro-2-isopropylhenzyl chloride 3-hromo-5-tert-but l-Lchlorohenzyl chloride 3-hromo-5-sec-butyl-Z-chlorobenxyl chloride 3-bromo-Z-chloro-S-isopropylhenzyl chloride 5-bromo-2.3-dichloro-4-isopropylbenzyl chloride 5 dichloro-4-isobutylhenzyl chloride 5 e-butyl-Z.3-dichlorobenzyl chloride 3 dichloro-4-ethylhen2yl chloride 3 -dichloro-4-ethylhenzyl chloride 3-hromo-4-sec-hutyl-Z.S-dichlorohenzyl chloride 3-hromo-4- c-hutvl-Z.o-dichlorobenzyl chloride 3 dichloro-o-propylhenzyl chloride dichloro-o-propylhenzyl chloride -dichloro-fi-isohutylbenzyl chloride romo-ZA-dichloro-6-isohutylbenzyl chloride romo-Z-tert-hutyH.4-dichlorohenzyl chloride -hromo-3.4-dichloro-2-l l.l.3.l-tetramethylpropyl)henzyl chloride 4-bromo-3.o-dichloro-Z-isopropylbenzyl chloride 4 hromo-2. -dichloro-o-isopropylhenzyl chloride 4'hromo-3 fi-dichloro-lisobutylbenzyl chloride dichloro-fi-isohutylbenzyl chloride 4-hromo-Z-sec-hutyl-B.S-dichlorohenzyl chloride 4-bromo-2-tert-hutyl-B.5 dichlorohenzyl chloride 4-hromo-2. -dichloro-3-isohutylhenzyl chloride dichloro-S-isobutylhenzyl chloride dichIoro-B-isopropylbenzyl chloride 4-bromo-2. dichloro-S-isopropylhenzyl chloride 4-bromo-2.6-dichloro-3-( l. l .2.2-tetrumethylpropyl )henzyl chloride 4-bromo-3-tcrt-hutyl-lfi-dichlorohenzyl chloride 3-bromo-5.o-dichloro-2-isobutylhenzyl chloride 5-hromo-2.J-dichloro-o-isohutyIbenzyl chloride 3-hromo-5.6-dichloro-Z-ethylhenzyI chloride S-hromo-Z 4-dichloro-o-cthylbenzyl chloride S-hromoc-hutyl .4-dichlorohenz \'l chloride B-hmmo-S-sec-hutyl .(w-dichlorohenzyl chloride 5-hromo-3-tert-butyl-ZA-dichlorobenzyl chloride 3'hromo-S-tert-butyl-Z,fi-dichlorohenzyl chloride 5hromo-Z-chloro-3-iodo-4-isobutylbenzyl chloride 3-hromo-Z-Chloro-S-iodo-4-isobut}lbenzyl chlorine 5-bromo-Z-chloro-3-fluoro-4-isopropylbenzyl chloride 3-hromo-2-chloro 5-fluoro-4-isopropylbenzyl chlorine 2.3.5trihromo-4-isopropylbenzyl chloride 3-hromo-2-chloro-4-iodo-5-isobutylbenzyl chloride S-hromo-IZ-chloro-4-iodo-3-isohutylbenzyl chlorine 3-hromo-2chloro-4-fluoro-S-isopropylbenzyl chloride 5-hromo-2-chloro-4-fluoro-S-isopropylbenzyl chloride .3.4tribromo5isopropylbenzyl chloride -hromo-Z-tert-hutyI-4.5-dichlorobenzyl chloride -bromo-2-tert'hutyl-4.fi-dichlorobenzyl chloride -bromo-2-sec-butyl-4.S-dichlorobenzyl chloride -bromo-2-sec-butyl-4. dichlorobenzyl chloride -bromo 4.5-dichloroisopropylbenzyl chloride -hromo-4.6-dichloro-Z-isopropylbenzyl chloride -hromo-5-tert-butyl-2.4-dichlorohenzyl chloride -b -b -b -h -h romo-S-tert-hutyl-Z.fi-dichlorobenzyl chloride romo-S-sec-butyL" 4-dichlorobenzyl Chloride romo-S-sec-hutyldichlorobenzyl chloride romo-2,4-dichloro-. sopropylhenzyl chloride romo-lfi-dichloro-S-isopropylhenzyl chloride 1 7 The following cyanobenzeneacetonitriles are prepared from the listed benzyl chlorides by the procedure of Example 4. Where isomeric mixtures are formed. the isomers are separated by chromatography.

and the product separates. The cooling bath is removed and stirring is continued for 15 minutes at 3035C. The mixture is then poured into ice water and the product collected, washed and dried.

TABLE VI Starting Material 5-bromo-2.3-dichloro-4-isopropylhenzyl chloride 5-hromo-2.3-dichloro--lisohutylhenzyl chloride 3hromo-2.5dichloro-4-ethylhenzyl chloride J-hromo-4-sec-hutyl-2.S-dichlorohenzyl chloride 3-hromo-Z.6-dichloro-4-ethylhenzyl chloride Il-hromo-4-sec-hutyl-Z.o-dichlorobenlyl chloride B-hromo-Z.5-dichloro-o-isohutylbenzyl chloride 3-hromo-2.5 dichloro-o-propylhenzyl chloride 3-hromo-2.4-dichloroo-propylhemyl chloride 3-hromo-Z.4-dichloro-6-isohutylhenzyl chloride S-hromo-2-tert-hutyl-3.4-dichlorohenzyl chloride 5-hromo-3.4-dichloro-Z-l l .l .2.Z-tetramcthylpropyl )henzyl chloride 4-hromo-3.o-dichloro-2-isopropylhenzyl chloride 4-hromo3.6-dichloro-Z-isohutylbenzyl chloride 4-hromo-2.3-dichloro-o-isopropylhenzyl chloride 4-hromo-2.3-dichloro-fi-isohutylhenzyl chloride J-hromo-Z-Sec-hutyl-3.5-dichlorohenzyl chloride 4-hromo-2-tert-hutyl-3.5-dichlorohenzyl chloride 4-hromo-2.5-dichloro-3-isohutylhenzyl chloride 4-hromo-2.5-dichloro-3-isopropylhenzyl chloride 4-hromo-2.3-dichloro-S-isohutylhenzyl chloride 4-hromo-2.3-dichloro-S-isopropylhenlyl chloride 4-hromo-2.6-dichloro3-( l.l.2.Z-tetramethylpropyl )henzyl chloride 4-bromo-3-tert-hutyl-2.6-dichlorohenzyl chloride 3-hromo-5.o-dichloro-Z-isobutylhenzyl chloride 3-bromo-5.h-dichloro-Z-ethylhenzyl chloride 5-hromo-2.4-dichloro-o-isohutylhenzyl chloride 5-hromo-2.4-dichloro-6-ethylhenzyl chloride 5-hromo-3-sec-hutyl-2.-l-dichlorohenzyl chloride 5-hromo-3-tert-hutyl-2.4-dichlorohenzyl chloride 3-hromo-5-sec-hutyl- .6-dichlorohenzyl chloride 3-hromo-5-tert-huty lh-dichlorohenzyl chloride S-hromo-Z-chloro-3-rodo-4-isobutylhenzyl chloride -hromo-Z-chloro-3-l'luoro-4-isopropylhenzyl chloride .5.-trihromo-4-isopropylhenzyl chloride -hromo-Z-terl-hutyl-4.5-dichlorohenzyl chloride -hromo-2-sec-hutyl-4.5-dichlorohenzyl chloride 3-hromo-4.5-dichloro-Z-isopropylhenzyl chloride 3-hromo-5-tert-hutyl-2.4-dichlorobenzyl chloride 3-hromo-5-sec-hutyl-2.4-dichlorohenzyl chloride 3-hromo-2.4-dichloro-S-isopropylhenzyl chloride EXAMPLE 6 4-Cyano-5-ethyl-2-nitrobenzeneacetonitrile A mixture of 146 parts of nitronium tetrafluoroborate and 600 parts of tetramethylene sulfone is stirred at l020C to produce a homogeneous suspension, and 198 parts of 4-cyano-3- ethylbenzeneacetonitrile is added portionwise in 20-30 minutes. As the reaction proceeds, the salt dissolves Product lichloro-S-cyano-4-isopropylhenzencacetonitrile ichloro-S-e ano--l-isohutylhenzeneacetonitrile d -dichloro-3-cyano-4-ethylhenxeneacetonitrile ec-hutyl-Z.5-dichloro-3-cyanohen'zeneacetonitrile dichloro-3 c\'ano-4-cthylhenzeneacetonitrile C-hlll \l-2.6-(llChlUI'O-3-C)'llI'lOhClllOllCLlCtZlOl']lll'lle d ichloro-S-cyano-fi-isohutylhenzeneacetonitrile ichloro-3-cyano-fv-propylhenzencacetonitrile In a similar manner, using the appropriate starting materials. one can prepare the compounds shown in the following table.

In many cases nitration yields mixtures of isomers.

These need not be separated for the purposes of this invention, but they can be separated by chromatography if desired.

TA B LE Vll Starting Material Product 4-cyano-3-methylhenzeneacetonitrile 4-cyano -5- ethyl-Z-nitrobenzeneacetonitrile 4 'opropyl-2-nitrobenzeneacetonitrile 4-cyano3-iso ropylhenzeneacetonitrile 4-cyano-3-isoliutylhenzcneacetonitrile 4-cyano-3-neopentylhenzeneacetonitrile 4-cyano-3-( LZ-dimethylpropyl )henzeneacetonitrile 3-hutyl-4-cyanohenzeneacetonitrile 3-sec-hutyl-4-cyanohenzeneacetonitrile 3-tert-hutyl-4-cyanohenzeneacetonitrile 4-cyano-3-propylhenzeneacetonitrile -l-cyano-2-methylhenzeneacetonitrile 4-cyano-2-isopropylhenleneacetonitrile 4-cyanoisobutylhenzeneaeetonitrile J-cyano-2-propylhenzeneacetonitrile Z-tert-hutyl-4-cyanohenzeneacetonitrile 2-sec-hutyl-4-cyanohenzeneacetonitrile 2-hutyl--l-cyanohenzeneacetonitrile S-cyano-Z-methylhenzeneacetonitrile 5-cyano-" ethylhenzeneacetonitrile S-cvano- 'opropylhenzeneacetonltrile fi-cyano-2-lsohutylhenzeneacetonitrile 2-butyl-S-cyanohenzeneacetomtrlle Z-tert-hulyl-S-cyanohenzeneacctonilrile 'ohutylQ-nitrobenzeneacetonitrile 4-cyano-. -neopentyl-2-nitrobenzeneacetonitrile 4-cyano-5-( 1.2-dimethylpropyl )-2-nitrobenzeneacetonitrile 5-hutyl-4-cyano-2-nitrohenzeneacetonitrile 5-sec-hutyl-4-cyanoZ-nitrohenzeneacetonitrile 5-tert-hutyI-4-cyano-2-nitrohenzeneacetonitrile 4-cyano-2-nitroS-propylbenzeneacetonitrile 4-cyano-2methyl'5 -nitrobenzeneacetonitrile 4-cyano-2-isopropyl-S-nitrohenzeneacetonitrile. 4-cyano-2-1sobutyl5-nitrohenzeneacetonitrile 4-cyano-5-nitro'l-propylhenzeneacetonitrile 2-tert-hutyl-4-cyano-5-nitrohenzeneacetonitrile -sec-butyl-4-cyano-S-nitrohenzeneacetonitrile -hutyl-4-cyano-5nitrohenzeneacetonitrile -cyano-2-methyl-3-nitrohenzeneacetonitrile -cyano-2-ethyl-3-nitrohenzeneacetonitrile -cyano-2-isopropyl3-nitrohenzeneacetonitrile -c \'ano-2-isohutyl-3-nitrobenzeneacetonitrile -hutyl-5-cyano-3-nitrohenzeneacetonitrile -tert-hutyl-S-cyano-3-nitrohenzeneacetonitrile m.p. 10|403c Starting Material Z-hromo-B-sec-but 2-bromo-3 -cyano--isopropyl-4.6-dinitrobenzeneacetonitrile Z-hutyl-4-chloro-5-cyano-3,o-dinitrobenzeneacetonitrile 3-tert-butyl-5-cyano-2 .6-dinitrobenzeneacctonitrile TABLE Vlll Continued Product Z-chloro-S-cyano-4-ethyl-3.o-dinitrohenzeneacetonitrile 4-hromo-5 -butyl-3-cyano-2.o-dinitrobenzeneacetonitrile -cyano-4.6-dinitrobenzeneacetonitrile 3-tert-butyl-5-cyano-2.4-dinitrohenzeneacetonitrile 5-tert-butyl-3-cyano-2.4-dinitrobenzencacctonitrile EXAMPLE 8 3-Brom0-2-tert-butyl-S-nitrobenzyl Chloride A mixture of 30 parts of 2-bromo-l-tert-butyl-4- nitrobenzenc and 30 parts of chloromethylmethyl ether is stirred vigorously while adding dropwise parts of 60 percent fuming sulfuric acid. The resultant mixture is allowed to stand until the apparent reaction ceases and is then poured into ice water. The solid is removed by filtration and washed with water to give 3-bromo-2- tert-butyl-5-nitrobenzyl chloride.

The benzyl chlorides listed in Table lX are prepared by the above procedure from starting materials disclosed in the preceding examples. Where isomer mixtures are obtained they can be used as such or separated into the component isomers by chromatography or distillation. The bcnzyl chlorides are converted to benzeneacetonitriles by reaction with cuprous cyanide according to the method of Example 2, shown in Table X.

TABLE IX collected and dissolved in IQ percent sodium hydroxide solution. The aqueous base solution is washed with ether and acidified, precipitating essentially pure 2- chloro-4-carboxy-6-propylphenylacctic acid.

Part B 4-Carboxy-2-chloro-3-nitro-6-propylphenylacetic Acid and 4-Carboxy-2-chloro-5-nitro-6-propylphenylacetic Acid To a mixture of 100 parts of 90 percent nitric acid and 200 parts of fuming sulfuric acid is added portionwise 20 parts of 4-carboxy-2-chloro-6- propylphenylacetic acid. The resulting solution is heated on a steam bath for 2 hours then poured into an ice-water mixture. THe resulting isomeric mixture of 4-carboxy-2-chloro-3-nitro-6-propylphenylacetic acid and 4-carboxy-2-chloro-5-nitro-6-propylphenylacetic acid is dried and used in Part C without further purification.

Starting Material Z-bromol -butyl-4-nitrobenzene Z-bromol -sec-butyl-4-nitrohenzene Z-bromol -isobutyl-4-nitrobenzene Z-bromol -isopropyl-4-nitrobenzene 2 hromol -eth \*l-4-nitrobenzene Z-bromol -methyl-4-nitrobenzene 2-bromo4-nitrol -propylhenzene l-bromo-Z-buIyl-B-nitrohenzene l-bromo-2-tert-hutyl-3-nitrobenzene l-bromo-2-sechutyl-B-nitrobenzenc l-bromo -isobutyl-3-nitrobenzene l-bromo---isopropyl-3nitrobenzene l-hromo-3-nitro-Z-propylbenzene l-bromo-2-butyl-4-nitrobenzene l-gromo-2-tert-butyl-4-nitrobenzene l -hromo-2-sec-hutyl-4-nitrohenzene l-hromo -isobutyl-4-nitrohenzene l-bromoopropyl-4-nitrobenzene l-bromo-4-n itro-Z-propylhenzene Z-bromol -butyl- -nitrohenzene 2-bromol -ethylnitrobenzene Z-bromol -methyl-3-nitrobenzene 2-bromo-3-nilrol 'propylhenzene 2-bromol -isobutyl-3-nitrohenzene 2'bromol -isopropyl- 3-nitrobenzene l-bmmo-2-nitro-4-propylhenzene I -bromo-4-hutyl-2-nitrobenzene l-bromo-4-tert-butyl-Z-nitrobenzene l-bromo-4 sec-butyl-Z-nitrobenzene l-bromo-4-isobutyl-Z-nitrobenzene l-bromo-4-isopropyl-2-nitrobenzene EXAMPLE 9 Product Part C Part A 4-Carboxy-2-chloro-6-propylphenylacetic Acid A mixture of 50 parts of 2-chloro-4-cyano-6- propylbenzeneacetonitrile and 200 parts of concentrated sulfuric acid is warmed on a steam bath for .l hour then poured into ice water. The resulting solid is 2-Chloro-4-chlorocarbonyl-3-nitro-6 propylphcnylacetyl chloride and 2-Chloro-4-chlorocarbonyl-5-nitro-6- propylphcnylacetyl chloride To 300 parts of thionyl chloride is added dropwise and with cooling 20 parts of the crude mixture of 2-chloro-4-carboxy- 3 (or 5 )-nitro-6- propylphenylacetic acids from Part B. The mixture is refluxed until no further evolution of gases is observed. The thionyl chloride is distilled and the residue vacuum dlsnned affordmg esscnuany pure 2 chlOmf4' nitro-o-propvlphenvlacetamide and 100 parts of phoschl0rocarbonyl-3-nltro-o-propylphenylacetyl chloride 5 H phorus oxuhlorrde is refluxed for I hour. The excess and the corresponding S-mtro isomer in separate frach v h I h] V d h V I tions. osp orus oxyc or e is remo\e I vacuum rsti tron and the residue is poured into ice water. The solid is collected, washed with water and recrystallized. affording essentially pure 2-chloro-4-cyano-3-nitro-6- m propylbenzeneacetonitrile. Part D Z-Chloro-4-cyano-5-nitro-6- propylbenzeneacetonitrile can be prepared by the same 4-Carboxamido-2-chloro-3-nitro-6- method. propylphenylacetamide H The nitrated cyanobenzeneacctonitriles of the follnto a cold solution of 10 parts of 2chloro-4- lowing table can be prepared by starting with the listed chlorocarbonyl-3-nitro-6-propylphenylacetyl chloride chlorinated cyanobenzeneacetonitriles. rather than in 200 parts of ether is passed dry ammonia. The resultwith 2-chloro-4-cyano-6-propylbcnzeneacetonitrile of ing precipitate is collected, stirred in 2% sodium hy Part A. droxide. filtered, washed with water and recrystallized. n those cases n which m r h n n i r i p iaffording pure 4-carboxamido-2-chloro-3-nitro-6- ble, separation can be effected by fractional distillation propylphenylacetamide. or chromatography at any convenient step. or the prod- By the same procedure. 4-carboxamido-2-chloro-5- uct can be isolated as a mixture of isomers and used nitro-6-propylphenylacetamide can be prepared. without separation.

TABLE XI Part E 2-Chloro-4-cyano-3-nitro-o-propylbenzcneacetonitrile A mixture of 5 parts of 4-carboxamido-2-chloro-3- Starting Material Product 2-chloro-4-cyuno-fl-isobutylbenzeneacetonitrile 2-chloro-4-cyano-6-propylbenzeneacetonitrile Z-tert-butyl-6-chloro4-cyanobenzeneacetonitrile Z-chloro-4-eyano-o-ethylhenzeneacetonitrile 6-chloro-4-eyano-2-ethyl-3-nitrohenzeneacetonitrile B'chIoro-S-cyano-Z-ethylhenzeneacetonitrile 3-chloro-5-cyano-2-isohutylhenzeneacetonitrile 3-chloro-5-cyano-Z-propylhenzeneacetonitrile 2-tert butyI-3-ehloro-5-cyanobenzeneacctonitrile Z-chloro-S-cyano-3-ethylhenzeneacetonitrile 2-chIoroS-cyano-lpropylhenzeneaeetonitrile Z-chloro-S-cyano 3-isobutylhenzeneaeetonitrile J-tert-butyl-2 ehlorod-cyanobenzeneacetonitrile 3-chloro-5cyano-Z-ethyl-4-nitrohenzeneacetonitrile -ehloro-S-cyano-'l-ethyl-6-nitrobenzeneacetonitrile -chIoro-5- -ano-Z-isobutyl-4-nitrohenzeneacetorlitrile -chloro 5-c\ no-2-isobutyl-o-nitrobenzeneacetonitrile -chloro-5-t.yano-4-nitro2-propylbenzeneacetonitrile 3-chlom-5-cyano-6-nitro-Z-propylhenzeneacetonitrile Z-tert-hutyl-3-chloro-5-cyano-4-nitrobenzeneacetonitrile Z-tert-butyl-3 chloro-S-cyano-6-nitrohenzeneacetonitrile Z-chloro-S-cyano-3-ethyI-4-nitrobenzeneacetonitrile 2-ehIoro5-e\'ano-3ethyl-fi-nitrobenzeneacetonitrile Z-chloro-S- yano-J-nitro-3-propylbenzeneacetonitrile Z-chIoro-S-cyano-6-nitro3-propylhenzeneacetonitrile Z-ehloro-5-cyano 3-isohutyl-4-nitrobenzeneacetonitrile 2-0hloro-S-cyano-3-isohutyl-6-nitrohenzeneacetonitrile 3-tert-butyl-Z-ehloro-S-cyano4-nitrobenzeneacetonitrile 3-tert-hutyl-Z-chloro-S-cyano-o-nitrobenzeneacetonitrile 2-chloro4eyano-3.h-diethyI-S-nitrobenzeneucetonitrile 2-chloro-4-cyano-S-nitro-3.fi-dipropylbenzeneacetonitrile 2-chloro-4- no-3.6-diisobutyl-5-nitrohenzeneacetonitrile 2-chloro-4-c no-3-ethyl-5-nitro-fi-propylbenzeneaeetonitrile 2-chloro-4-cyano-3-ethyl-6-isohutyl-5-nitrobenzeneacetonitrile Z-chloro-4-cyano-6-isobut l-3-isopropyl-5-nitrobenzeneacetonitrile 2-chloro-4-cyano-6-isohutyl-5-nitro-Z-propylbenzeneacetonitrile 2 chloro-4-cyano-3-isohutyl-5-nitro-6-propylbenzeneacetonitrile fi-tert-hutyl-Z-chloro-4-cyano-3-isohutyl-S-nitrobenzeneacetonitrile 3-chloro'4-eyano-2.o-diethyl-S-nitrohenzeneacetonitrile 3-chloro-4-cyano-2.o'diisohutyl-5-nitrobenzeneacetonitrile 3-chloro-4-cyano-5-nitro-Z.6-dipropylhenzeneacetonitrile 2-tert-butyl-3-chloro-4-cyano'5-nitro-6-propylhenzeneacetonitrile Z-tert-butyl-B-chloro-4-cyano-6-isobutyl-5nitrobenleneacetonitrile 3-chloro-5-cyano'2.4-diethyl-6-nitrobenzeneacetonitrile 3-chloro-5-cyano-. .4-diisohutyl-6-nitrobenzeneacetonitrile 3-chloro- -cyano-o-nitro-2.4-dipropylhenzeneucetonitrile 3-chloro-5-cyano-Z-ethyl-4isohutyl-6-nitrobenzeneacetonitrile Z-terbbutyl-Il-chloro-5-cyano-6-nitro-4-propylbenzeneacetonitrile 3-chloro-5-cyano-2.o-diethyl-4-nitrobenzeneacetonitrile 3-bromo-5-cyano- .6-diisobutyl4nitrobenzeneacetonitrile 3-chloro-5cyano-2,6-diisobutyl-4-nitrobenzeneaeetonitriIe 2.6-di-tert-butyl-3-chloro-5-cyano-4-nitrobenzeneacetonitrile 2-tert-butyl-3-ehIoro5-cyano-6-isobutyl-4-nitrohenzeneacetonitrile 6-tert-hutyl-3-chIoro-5cyano-2-isohutyl4nitrobenzeneacetonitrile Z-chloro-S-cyano-4-nitro-3.fl-dipropylbenzeneacetonitrile 2-chloro-5-cyano-3.li-diisobutyl-4-nitrobenzeneacetonitrile 2-chloro-5-cyano-3.(i-diethyl-4-nitrobenzeneaeetonitrile 3-tert-butyl-Z'chloro-i-cyano-6-ethyl-4-nitrobenzeneacetonitrile 3 tert-butyl-Z-chloro- -cyano-4-nitro-o-propylbenzeneacetonitrile 6-terthutyl-Z-chloro-S-c 'ano-3 isobutyl-4-nitrobenzeneucetonitrile wwww Starting Material EXAMPLE 1l 2-Bromo-l,4-diisopropylbenzene To a one-liter flask containing 243 parts of p-diisopropylbenzene. 300 parts of carbon tetrachloride and 2.5 parts of iron powder is added dropwise 240 parts of bromine and sufficient carbon tetrachloride to make 180 parts ofa solution during seven hours at a temperature of C. The solution is decanted from the residual ferric bromide and washed twice with 3N HCl. The carbon tetrachloride is removed under reduced pressure. A solution of 40 parts potassium hydroxide in two hundred parts of ethyl alcohol is added and refluxed 0.5 hr. The solution is poured into water, separated. washed with dilute hydrochloric acid, dilute sodium bisulflte solution and water, and dried. The solvent is removed and the 2-bromo1,4-diisopropylbenzene distilled. bp 142C at mm, h 1.5292.

By substituting the following alkylbenzenes for p-diisopropylbenzene, the following haloalkylbenzenes are made:

TABLE Xlll Starting Material TABLE x11 -C0ntinued Product 2-hromo-3-cyano-o-isobutyl-5-nitrohenzeneacetonitrile 2-chloro-3-cyano-fi-isobutyl-S-nitrobenzeneacetonitrile 2-hromo-o-hutyl-3-cyano-5nitrohenzeneacetonitrile (v-tert-butyl-Z-chloro-3-eyano-5-nitrobenzeneacetonitrile Z-chloro-3-cyano'5-nitro-6-tert-pentylbenzeneacetonitrile 4-chloro-5-cyano-3-ethyl-6-nitrobenzeneacetonitrile 4-chloro-5-cyano-6-nitro-3-propylbenzeneacetonitrile 4-bromo-S-cyano-fi-nitrod-propylhen zeneacetonitrile 4-chloro-S-cyano-B-isobutyl-6 nitrobenzeneacetonitrile 4-hromo5-cyano-3 ohutyl-(i-nitrobenzeneacetonitrile 5-cyano-4-fluoro-3-isohutyl-6-nitrobenzeneacetonitrile 3-tert-butyl-4-chloro-5-cyano-6-nitrobenzeneacetonitrile 4-bromo-3-tert-hutyl-5-cyano-6-nitrobenzeneacetonitrile EXAMPLE l2 2-F1uoro-l,4-diisobutylbenzene (Org. React. Vol V, p 203) To 124 parts of 6N hydrochloric acid is added 48.8 parts of 2,5-diisobutylaniline. The mixture is cooled to 0 and a cold solution of 17.3 parts of sodium nitrite in water is added slowly, keeping temp. at 0. A cold solution of parts of ammonium fluoroborate in parts of water is added with vigorous stirring. After /2 hour, the precipitate is collected, washed with 25 parts cold 5 percent ammonium fluoroborate solution, 30 parts cold methanol and ether. The 2,5- diisobutyIbenzenediazonium fluoroborate is air dried. The salt is placed in a flask with tube connecting to a second cooled flask and heated until decomposition begins. Sufficient heat to maintain gentle decomposition is continued. When decomposition is complete, the 2- fluoro-l,4-diisobutylbenzene is taken up in ether, washed with dilute sodium hydroxide and water and dried. Removal of the ether gives 2-fluoro-l.4- diisobutylbenzene which can be purified by distillation Product 3-bromo-4-isobutylisopropylbenzene obutylisopropylbenzene p-isohutylpropy[benzene p-sec-hutylisobutylhenzene m-sec-butylisohutylhenzene p-ethylisobutylhenzene p-di-sec-butylbenzene m-di-sec-butylbenzene p-tert-hutylisopropylhenzene m-tert-butylisobutylhenzene m-diisopropylhenzene p-diisobutylbenzene di-tert-hutylbenzene p-tert-hutylethylhenzene -sec-hutylethylhenzene Z-dimethylpropyl )ethylhenzene 2-dimeth \'lpropyl )propylbenzene Z-dimethylpro yl)isohutylbenzene -tert-butylisohutylbenzene -ethyl-tert-pentylhenzene -fluorol .S-diisopropylbenzene 44 1.2-dimethylpropyl l -ethyl-2-fluorohenzene 4-lert-hutyltoluene m-ethyl-tert-pcntylhenzene p'methyH 1.1.2.Z-tetramethylpropyl)henzene p-cth vl-( l.l.2.Z-tetramethylpropyl )henzene m-diethylbenzcne m-diisobutylhenzene p-ethylneopentylbenzene 2-hromo-4 obutylpropylbenzene 2-hromo-4-sec-butylisobutylbenzene 1-bromo-4-sec-hutyl-Z-isobutylbenzene Z-bromol -et'hyl-4-isobutylhenzene Z-bromol .4-di-sec-butylhenzene 1-hromo-2.4-di-sec-butylbenzene 2-hromo-4-butylisopropylbenzene l-hromo-4-tert-butyl-Z-isobutylbenzene 4-bromol .3-diisoprop \'lhenzene lbromo-l .4-diisobutylbenzene. hp 72% at (1.1mm l.4-di-tert-butyl-Z-chlorobenzene 2-hromo-4-tert-butylethylhenzene 2-bromo-4-sec-butylethylbenzene 2-bromo-4-( 1 .2-dimethylpropyl )ethylhenzene 2-hromo-4-t 1 .Z-dimethylpropyl)propylhenlene 2-hromo-4-( l .Z-dimethvlpro yHisohutylbenzene 2-hromo-4-tert-butylisohutyl enzene Z-hromo- 1 -eth \'l-4-tert-pentylbenzene 5-bromo-2-fluorol .4-diisohutylhenzene 4-bromo-2-fluorol .S-diisopropylbenzene 5-hromo-4-( l .2-dimeth \'lpropyl l -ethyl-2-fluorobenzene lhromoktert-butyltoluene 4-hromo-3-ethyl-ten-pentylbenzene I Z-hromo1-meth \l-4-( 1.1 .2.2-tetramcthylpropyl )benzene v 2-hromol -ethyl-4-( l, l .2.2-tetramethylpropyl )henzene Z-hromol .3- iethylbenzene Z-bromol ,3-dusobutylbenzene B-bromo-4-ethylneopentylbenzenc under reduced pressure. a total time of 6.5 hrs. The mixture is cooled and In a similar manner the following compounds are prewashed with hydrochloric acid. dilute sodium bicarpared: bonate, and waterv After drying, the 4-bromo-2.5-diiso- TABLE XlV Starting Material Product 2.4-diisopropylaniline 4-fluoro-l ,3-diisoprop \lbenzene 54 l.Z-dimeth \'lprop \l J-Z-ethylaniline 44 I .Z-dimethylpropyl l -ethyl-2-fluorohenzene 2.4-diisopropylaniline 4-iodol .3-diisopropylbenzene Z-ethyl-S-t l.I 2.2-tetramethyl )aniline l-ethyl-2-fluoro4-( 1.1.ZLtetrameIhyI)henzenc 2.5-diisopropylaniline Z-fluorol ,4.-diisopropylhenzeuc Z-isohutyl-5-isopropylaniline Z-lluoro-l-isohutyl-4-isopropylbenzenc Stert-hutyl-Z-isopropylaniline 4-tert-hut \l-2-fluorol -isopropylhenzene EXAMPLE l3 propylbenzyl chloride is distilled, bp 9I93C at 0.5

mm. 4-Bromo-2,5-diisopropylbenzyl Chloride By substituting the following haloalkylbenzenes for In a flask is placed 36 parts of Z-bromo-lA-diisopro- 2-br0mo-l.4-diisopropylbenzene, the following haloalpylbenzene, parts of paraformaldehyde and 20 parts kylbenzyl halides are made.

TABLE XV Starting Material Product 3-hromo-4isobutylisopropylbenzene 4-hromo5-isohutyl-Z-isopropylhenzyl chloride 3-hromo-4-isobutylisopropylbenzene 3-bromoisohutyl-S-isopropylhenzyl Chloride 2-bromo-4-isobutylpropylhenzene 4-hromo-Z-isohutyl-S-propylbenzyl chloride 2-bromo-4-sec-butylisobutylhenzene 4-hromo-2-sec-hutyl-5 isohutylbenzyl chloride l-bromo-4-sec-butyl-2-isohutylbenzene 5-hromo-Z-sec-hutyl-4-isohutylbenzyl chloride Z-bromol -ethyl-4-isohutylbenzene 4-hromo-S-ethyl-Z-isobutylbenzyl chloride Z-bromol .4-di-sec-hutylhenzene 4-hromo-2.5-di-sec-butylbenzyl chloride l-bromo-2.4-di-sec-butylhenzene 5-hromo2.4-di-sec-butylbenzyl chloride 2-bromo-4-tert-butylisopropylhenzene 4-hromo-2-tert-hutyl -isopropylhenzyl chloride 4-tert-butyl-2-chloroisopropylhenzene 2-tert-butyl-4-chloro- -isopropylhenzyl bromide 4-bromo- I .3-diisopropylbenzene 5-hromo-2.4-diisopropylbenzyl chloride Z-hromo-l.4'diisohutylbenzene 4-bromw2.5 diisobutylbenzyl chloride. h.p. l()7-I l()C at (H mm S-hromo-Z-fluorol .4diisobut \lhenzene 5-hromo-2-fluoro-3.6-diisobutylhenzyl Chloride 4-hromo-2-fluorol .5-diisopropylhenzene 5-hromo-3-lluoro-2.o-diisopropylbenzyl chloride 5-hromo4-( l.Z-dimethylpropyll-l-ethyl-2-fluorobenzenc 5-bromo-6-( LZ-dimethylpropyl )-3-ethyl-2-fluorohenzyl chloride 2-hromo-4 tert-hutyltoluene 3-hromo-5-tert-butyLZ-methylhenzyl chloride 4-hromo-3-ethyltert-pentylhenzene 5-hromo-4-ethyl-Llert-pentylhenzyl chloride of zinc chloride. A stream of dry hydrogen chloride is In some cases, chloromethylation of the bromoalkylpassed in with stirring. and the temperature rises to benzenes gives mixtures of isomers. These may be sepa- C. The temperature is maintained at 65C for three rated by careful distillation or by chromatography. but hours and is increased to C. Additional amounts of usually the mixture is used in subsequent reaction. The 15 parts of paraformaldehyde and 15 parts ofzinc chlo- 45 following compounds give the indicated mixtures when ride are added, and the reaction is continued at for chloromethylated:

TABLE XVl Starting Material Product Z-hromol .4-di-tert-hutylhenzene 3-bromo-2.5-ditert-hutylhenzyl chloride 4-hromo-Z.5-di-tert-hutylbcnzyl chloride 2-bromo-4-tert-hutylethylhenzene 3-hromo-5-tert-hutyl-2-ethylhenzyl chloride 4-hromo-2-tert-hutyl-5-ethylhenzyl chloride. hp. 92 C/().() mm Z-hromo--l-scc-hutylelhylbenzene 3-hromo-5- c-hutyl-2-ethylhenzyl chloride 4-hromo'2- c-hutyl-5-ethylhenzyl chloride Z-hromo-J-t l.Z-dimethylpropyl)ethylhenzene 3-hromo-5-( l.Z-dimethylpropyl)-2-ethylhen7yl chloride 4-hromo-2-( l.Z-dimethylpropyll-5-ethylhenzyl chloride 2-hromo-4-( l.l'tlimcthylpropyl)propylhenzene 3-hromo-5-( I.Z-dimethylpropyll-l propylhenzyl chloride 4-hromo-2-( LZ-dimethylpropyl l-5-propylhenzyl chloride 2-hromo-4-( l.Z-dimethylpropyl)isobutylhenzene 3-bromo-5-( l.2dimethylpropyl)-2-isohutylhcnzyl chloride 4-hromo-2-( LZ-dimethylpropyl )6-isohutylhenzyl chloride 2-hromo-4-tert-hutylisohutylhenzene B-hromo-S-tert-butylisohutylhenzyl chloride 4-hromo-2-tert-butylisohutylhenzyl chloride Z-hromol -ethyl-4-tert-pentylhenzene 3-hromo-Z-ethyl-S'tert-pentylhenzyl chloride 4-hromo-5-ethyl-2-tert-pentylhenzyl chloride 2-hromo-l-meth \'l-4-( l.l.2.Z-tetramethylpropyl)henzene 3-hromo-2-methyl-5-t l.l.2.Z-Ietramethylpropyl)henzyl chloride 4-hromo-5-methyl-24 l l .2.Z-tetramethylpropyl )henzyl chloride 2-hromo-l-ethyl-4-t l-ethyl-l-methylpropyl)henzene 3-hromo-2-ethyl-5-t l ethyl-l-methylpropyl)henzyl chloride 4-hromo-5-ethyl-2-( i-ethyll -methylpropyl )henzyl chloride 3-hromo-4-ethylneopcntylhenzene 3-hromo-Z-ethyI-S-neopcntylbenzyl chloride 4hromo-5-ethyl-l-neopcntylbenzyl chloride Z'hromol ,3-dicthylhenzene 3bromo-Z.4-diethylbenzyl chloride 4-hromo-3.S-diethylbenzyl chloride Z-hromol .3-diisohutylhenzene 3-hromo-2.4-diisohutylhenzyl chloride 4-hromo-3.S-diisohutylhenzyl chloride EXAMPLE 14 2,4-Dibromo-3.o-diisobutylbenzyl Chloride To a solution of 23.8 parts of 2,5-diisobutylbenzyl chloride in 50 parts of carbon tetrachloride there is products are obtained:

carbon tetrachloride is removed. and the 4-bromo-2- chloro-3,o-diisopropylbenzyl chloride is recovered.

By replacing the 4-bromo-2,S-diisopropylbenzyl chloride with the following benzyl chlorides, these TABLE XVlll Starting Material 4-hromo-2-ethyLS-isohutylbenzyl chloride 4-bromo-5-( l.2-dimethylpropyl )-2-propylhen7. \'l chloride 3-iodo-2.6-diisopropyl-4-methylbenzyl chloride 4-hromo-2-isopropyl-5-( l.l .2.2-tetramethylpropyl )henzyl chloride 4-hromo-S-isobutylQ-isopropylbenzyl chloride 3-bromo-2.6-di-tert-hutyl-J-methylbenzyl chloride Product 4-hromo-2-chloro-6-ethyl-3-isobutylhenzyl chloride 4-hromo-2-chloro-3-( LZ-dimethylpropyl l-fi-propylbenzyl chloride 3.5-diiodo-2.o-diisopropyl-4-methylhenzyl chloride 4-hromo-Z-chloro o-isopropyl-3-( l.l.2.Z-tetramethylpropyl )henzyl chloride 4-hromo-2-chloro-3-isohutyl-(visopropylbenzyl chloride 3-bromo-2.6-di-tert-butyl-S-chloro-4-methylbenzyl chloride For unsymmetrical alkylbenzenes. a different isomer is obtained if one first chloromethylates and then brominates.

EXAMPLE l6 2-lsobutyl-5-isopropylbenzyl Chloride In a flask there are placed l76 parts of p-isopropylisobutylbenzene. parts of paraformaldehyde, and 15 parts of zinc chloride. A stream of hydrogen chloride is passed into the mixture, and the temperature is increased to 65C. After the mixture is saturated TABLE XVII Starting Material Product 2.5-dipropylbenzyl chloride 2.4-dihromo-3,6-dipropylhenzyl chloride 2-isohutyl5-isopropylhenzyl chloride 2.4-dibromo-6-isohutyl-3-isopropylhenzyl chloride 2.S-diisopropylbenzyl chloride 2.4-dihromo-3.fi-diisopropylbenzyl chloride 2.5-di-tert-hutylbenzyl chloride 2.4-dihromo-3.o-di-tert-butylbenzyl chloride 2.5-di-sec-butylbenzyl chloride 2.4-dihromo-3.o-di-sec-butylhenzyl chloride EXAMPLE l5 4-Bromo-2-chloro-3,o-diisopropylbenzyl Chloride To a solution of 29 parts of 4-bromo-2,S-diisopropylbenzyl chloride in 50 parts of carbon tetrachloride there is added 1.0 part of iron powder. To the mixture, cooled to 0 and stirred, there is added 7.8 parts of chlorine during 2 hr. Stirring is continued for 2 hours;-

the solution is washed with dilute hydrochloric acid, so-

dium bicarbonate solution, and water. After drying. the.

Starting Material with hydrogen chloride. stirring is continued at -75C for 3 hours. The mixture is cooled and washed with hydrochloric acid. sodium bicarbonate solution, and water. After drying,.the product is distilled. The first fraction is the unchanged starting material; the higher boiling material. -80C at 0.05 mm. is the desired Z-isobutyl-S-isopropylbenzyl chloride.

Using the indicated starting alkylbenzenes in the same molar amounts as in Example 16. the following compounds are prepared:

TABLE XIX Product Zisobutyl-4-isopropylben2ylchloride 5-isohutyl2-propylhenzyl chloride 4-isohutyI-Z-propylbenzyl chloride isohutylhcnzyl chloride 4-sec-hutylisobutylbenzyl chloride Z-ethyl-S-isohutylbenzyl chloride 5-tertbutyI-Z-isopropylbenzyl chloride 4-tert-butyl-2-isopropylbenzyl chloride 5-tert-hutyLZ-ethylhenzyl chloride S-scc-butyl-Z-ethylhenzyl chloride 5-( l.2-dimethylpropyl )-2ethylhenzyl chloride 5-( LZ-dimethylpropyl )-2-propylbenzyl chloride 5-( l.2-dimethylpropyl )-2-isohut vlbenzyl chloride 5-tert-butyl-Z-isobutylhenzyl chloride Z-cthyl-S-tert-pentylhenzyl chloride 2.4-d|ethylhenzyl chloride 2.4-diisohutylhenzyl chloride 2.6-dipropylhenzyl chloride 2,6-diisohutylhenzyl chloride 2-ethyl-5-( LLZ-trimethylpropyl )benzyl chloride 2-propyl-5-( l.l .2.Z-tetramethylpropyl )benzyl chloride 2-methyl-4-( l.l .Z-trimethylpropyl )hcnzyl chloride EXAMPLE l7 4-Bromo-2-isobutyl-S-isopropylbcnzyl Chloride In a flask are placed 225 parts of 2-isobutyl-5 isopropylbcnzyl chloride, 300 parts of carbon tetrachloride EXAMPLE l8 and 2.5 parts of iron powder. Bromine (I60 parts) 1n I parts of carbon tetrachloride is added dropwise 2'6'D'bmmo4'chlommethyl'3-5'dllsopmpylphenol during 7 hr. The solution is washed twice with hydro- Three hundred thirty-six parts of 2.6-dibromo3.5- chloric acid then with sodium bicarbonate solution, didiisgpropylphenol [prepared as de ribed in CamuL J. lute sodium bisulfite solution, and water. The solution Chem V L 41 1653 (1963)] is allowed to react is dried. the carbon tetrachloride removed and the 4- With 130 arts of Chlommeth 1 math 1 ether and 80 bromo-Z-isobutyl-S-isopropylbenzyl chloride distilled p i i under reduced prcssurc parts of stannlc chloride in 400 parts of carbon disul- In a similar manner. using the designated benzyl chlofide Under general dit SCI forth n "O ganic R rides, the following compounds are made: actions." Vol. 1. p. 68 and 69. The reaction mixture is TABLE XX Starting Material 2-isobutyl-4-isopropylbenzyl chloride 5-isobutyl-Z-propylbenzyl chloride 4-isohutyl-Z-propylhenzyl chloride S-sec-butyl- -isobut \-lhenzyl chloride 4-sec-butylisobutylbenzyl chloride Z-ethyl-S-isobutylhenzyl chloride S-tert-butyl-2-isopropylhenzyl chloride Product -|sobutylbenz \'l chloride isobutylbenzyl chloride 4-tert-butyl-Z-isopropylbenzyl chloride 2.4-diisopropylbenzyl chloride 24-diisopropylbenzyl chloride 4-hromo-5-tert-butyI-Z-isopropylbenzyl chloride 6-hromo-4-tert butyl-IZ-lsopropylhenzyl chloride 5-chloro-2.4diisopropylhenzyl chloride I 5-iodo-2.4-diisopropylhcnzyl chloride 2-ethyl-5-( I. l .Z-trimethylpropyl )benzyl chloride 2-propyl-5-( l. l .2.2-tetramethylpropyl )benzyl chloride 2-methyl-4-( LLZ-Irimethylpropyl )henzyl chloride -l-bromo-.'Z-ethyl-5-( l. l .Z-trimethylpropyl )henzyl chloride 4-hromo-2-propyl 5-( l. l tll-tetramethylpropyl )benzyl chloride 5-hromo-2-methyl-4( l. l .Z-trimethylpropyl )henzyl chloride In some cases, bromination of the alkylbenzylchlopoured on ice, and the organic layer is separated and rides gives mixtures of isomers which can be separated by careful distillation or chromatography, but usually the mixture is adequate for the intended purpose. The following compounds give the indicated mixtures when brominated:

TABLE XXI dried over anhydrous calcium sulfate. The solvent is allowed to evaporate and the residue is crystallized to give a pure sample of the title compound. Chloromethylation of the following monohaloor dihalodialkyl- Starting Material S-tert-butyl-2-ethylhenzyl chloride 5-scc-hutyl-2-ethylhenzyl chloride 5-( l.2-dimethylpropyl)-2-ethylhenzyl chloride 5-( l.Z-dimethylpropyl)-2-propylbenzyl chloride 5-( l.Z-dimethylpropyl)-2-isohutylbenzyl chloride 5-tert-hutyl-2-isohutylhenzyl chloride 2-ethyl-5tert-pentylhenzyl chloride ZA-diethylhenzyl chloride 2.4-diisohutylhcnzyl chloride 4-isohutyl-Z-propylhenzyl chloride lo-dipropylhenzyl chloride 2.6-diisohutylhenz \'l chloride Product 4-hromo-5-tert-hutyLZ-ethylbenzyl chloride 3-bromo-5-ten-butyl-2-ethylhenzyl chloride 4-bromo-5-sec-butyl-2-cthylhenzyl chloride 3-hromo-S-sec-hutyl-2-ethylbenzyl chloride 4-hromo-5-( l.Z-dimethylpropyl)-2-ethylhenzyl chloride 3-bromo-5-( l.Z-dimethylpropyl)-2-ethylhenzyl chloride 4-bromo-5-( LZ-dimethylpropyl )-2-propylhenzyl chloride 3-bromw5-( l.2 dimcthylpropyl )-2-propylhenz vl chloride 4-hromo-5-( Lldimethylpropyl )-2-isohutylbenzyl chloride 3-bromo-5-( LZ-dimethylpropyl )-2-|sohut \'lbcn7. \'l chloride 4-hromo-5-tert-butyl-2-isohutylbenzyl chloride 3-bromo-5 tert-butyl-Z-isobutylhenzyl chloride 4-hromo-2-ethyl-5-tert-pcntylhenzyl chloride 3-hromo-Z-ethyl5-tert-pentylhenzyl chloride S-hromo-Z.4-diethylbenzyl chloride 3-hromo-2.4-diethylhenzyl chloride 5-hromo2.4-diisohutylhenzyl chloride 3-hromo-2.4-diisobutylhenzyl chloride 5-bromo-4-isohutyl-2-propylhenzyl chloride 3-hromo-4-isobutyl-l propylhenlyl chloride 3-bromo-2to-dipropylhenzyl chloride 4-hromo-2.o-dipropylhenzyl chloride 3-hromo-Z,6-diisohutylhenzyl chloride 4-hromo-2.o-diisohutylbenzyl chloride 37 38 phenols gives the corresponding chloromethyl deriva- 1 resorcinols gives the corresponding chloromethyl detives. rivatives.

TABLE XXII Starting Materials Product 2.4-dichIoro-3.o-diisopropylphenol 2.4-dichloro-5-chIoromethyl-3.6-diisopropylphenol 2.3-dichloro-4.o-diisopropylphenol 2.3-dichl0ro-5-chIorometh}'I-4.o-diisopropylphenol 2.6-dichloro-3,S-diisopropylphenol 2.6-dichloro-4-chloromethv -diisoprop vlphenol di-tert-hutyl-2.6-dichlorophenol 3- rt-butyl-2.6'dichloro-5-ethylphenol EXAMPLE 19 4.5-dichloro-3-chlorometh3 -diisopropylphenol 2-chloro-4-chloromethyl-3.S-diisopropylphenol 2-chloro-4-chloromcthyl-lo-diisopropylphenol 2-chloro-3-Chl0romethyl4.6-diisopropylphenol Z-bromoA-chloromethyI-3.(i-diisopropylphenol 4-hromo-2-chloromethyl-3.6-diisopropylphenol 4-chloro-3chloromethyl-lo-diisopropylphenol 3-tert-hutyl-2.6-dichloro-4-chloromethyl-S-isopropylphenol 6-dichloro-4-chloromethyl-. sopropylphenol 2.6'dihromo-. isobutylA-chloromethyl-S-isopropylphenol 3.5-di-sec-hutyl-Z.6-dichloro-4-chloromethylphenol .o-dichl0ro-4-ehloromethyl-3.5diisohutylphenol -tert-hutyl-2.6-dichloro-4-chloromethyI-B-isohutyl phenol .5-di-tert-butyl-2.6-dichloro-4-chloromethylphenol tert-butyl-2.6-dichIoro-4-chloromethyl-S-ethylphenol EXAMPLE 20 S-Bromo-2-chloromethyl-3,o-diisopropylhydroquinone Two hundred seventy-three parts of 3-bromo-2,5- diisopropylhydroquinone is allowed to react with 130 parts of chloromethylmethyl ether and 80 parts of stanl-Bromo-2,6-diisopropylbenzene A solution of 262 parts of triphenylphosphine in 750 parts of acetonitrile is brominated with 160 parts of nic chloride in 400 parts of carbon disulfide under genw bromine at room temperature. The solvent is evapoeral conditions set forth in Organic Reactions, Vol. 1, p. 68 and 69. The reaction mixture is poured on ice, and the organic layer is separated and dried over anhydrous calcium sulfate. The solvent is allowed to evaporated, and to the residue is added 178 parts of 2,6- diisopropylphenol. The mixture is heated at 200C as described in J. Am. Chem. Soc. 86, 464 (1964). The product is distilled under reduced pressure and then rate and the residue is crystallized to give a pure sample *5 fractionated at 0.1 mm Hg.

of the title compound. Chloromethylation of the following monohaloor dihalodialkylhydroquinones or The following compounds are made by appropriate substitution in the above procedure.

TABLE XXIII Starting Material 2-hromo-3.5-diisopropylhydroquinone 5-hromo-4.6-diisopropylresorcinol 3-hromo-5 tert-butyl-Z-isopropylhydroquinone 3-bromo-5-see-butyl-Z-isopropylhydroquinone 3-bromo2isobutyl-5-isopropylhydroquinone 3-bromo-2.5-di-sec-hutylhydroquinone 3-bromo-2 .5 -diisohutylhydroq uinone 3-hromo-2.S-di-tert-butylhydroquinone 3-hromo-5-tert-hutyl-2-isobutylhydroquinone 3-bromo-5-tert-hut 'l-Lethylhydroquinone Starting Material ,6-diisopropylphenol -dichloro-5-chloromethy 4.o-diisopropylphenol S-diisopropylphenol -dichloro-3-chloromethyl-2,6-diisopropylphenol yl-S-isopropylphenol 3-sec-butyl-2.h-dichloro-4'chloromethyl-S isopropylphenol Product Z-bromo-(a-chloromethyl-3.5 -diisopropylhydroquinone S-bromo-Lchloromethyl -diisopropylresorcinol 3bromo-5-tert butyl-6-dibromomethyl-2-isopropylhydr0quinone 3-bromo-5-sec-hutyl-6-chloromethyI-Z-isopropylhydroquinone 3-bromo-6-chloromethyl-2-isobutyl-5-isopropylhydroquinone 3-bromo-2.5-di-sec-but 'l-6-chloromethylhydroquinone 3-hromo-6-chloromethyl-Z.S-diisobutylhydroquinone 3-hromo-2 .S-di-tert-butyl-6-chloromethylhydroq uinone 3-brom0-5-tert hutyl-fi-chloromethyl-"-isohutylhydroq uinone 3-hromo-5-tert-hutyl-o-chloromethyl- -ethylhydroquinone TABLE XXIV Product l-chloro-2,o-diisopropylhenzene 5-hromo-2.4-dichloro-3.fi-diisopropylbenzyl chloride 5bromo-3.4-dichIoro-Z.o-diisopropylbenzyl chloride 4-bromo-3,5-dichloro-2.o-diisopropylbenzyl chloride 5-bromo-2.3-dichloro4.6-diisopropylbenzyl chloride 4hromo-3-chloro-2,o-diisopropylbenzyl chloride 4-hromo-3-chloro-3.6-diisopropylhenzyl chloride 3-hromo-2chloro'4,6-diisopropylhenzyl chloride 3'hromo-4-chloro-Z.S-diisopropylbcnzyl chloride 5-hromo-2-chloro-3 .o-diisopropylhenzyl chloride 5-bromo-24:hloro-4.6-diisopropylhenzyl chloride 4-bromo-2-tert-hutyl-3.5-dichloro-o-isopropylhenzyl chloride 4-bromo-2-sec-butyl-3.5-dichloro-o-isopropylhenzyl chloride 3.4.5-trihromo-Z-isohutyl-o-isopropylhenzyl chloride 2.fi-dihromo-3-isobutyl-4-chloromethyl-fi-lsopropylphenol 3.5-di-sec-hutyl-2.6-dichloro-4-chloromethylphenol 4-hromo-2.6-di-sec-butyl-3.S-dichlorohenzyl chloride 2.6-dichloro-4-ehloromethyl-3.S-diisobutylphenol 4-bromo-3.5-dichloroQ.odiisohutylbenzyl chloride 5-tert-butyl-2.6-dichloro-4-chloromethyl-3-isohutylphcnol 4-bromo-2-tert-hutyl-3.5-dichloro-(i-isohutylbenzyl chloride 3.5-di-tert-hutyl-2.6-dichloro-4-chloromethylphenol 4-bromo-2.6-di-tert-hutyl-Il.S-dichlorohenzyl' chloride 3 tert-butyl-2.6-dichloro-4-chloromethyl-5-ethylphenol 4'bromo-2-tert-hutyl-3 S-dichloro-o-ethylbenzyl chloride 

1. AN HERBICIDAL COMPOSITION CONSISTING ESSENTIALLY OF A CARRIER AND AN EFFECTIVE AMOUNT OF AT LEAST ONE COMPOUND HAVING THE FORMULA
 2. An herbicidal composition of claim 1 wherein R5 and R6 are hydrogen.
 3. An herbicidal composition of claim 2 wherein the compound is 4-cyano-2,5-diisopropyl-benzeneacetonitrile.
 4. A method of controlling undesirable vegetation, said method comprising applying to the locus of said undesirable vegetation herbicidally effect amount of at least one compound having the formula:
 5. The method of claim 4 wherein R5 and R6 are each hydrogen.
 6. The method of claim 5 wherein the herbicidal compound is 4-cyano-2,5-diisopropylbenzeneacetonitrile. 